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Back when Pokémon Platinum came out, the Rotom Appliance Formes had a gigantic impact on the metagame. Rotom was a Pokémon with an awesome unique typing, an even better ability, and a pretty awesome movepool, hampered only by the fact that its stats were pretty unequivocably terrible. 50/77/77 defenses weren't walling anything in OU, and 95 Special Attack just didn't pay the bills. With the upgrade to Rotom-A, Rotom picked up impressive boosts to its defenses and Special Attack, as well as a couple of mutually exclusive new coverage moves that let it threaten a couple new things it couldn't before. Its Ghost typing quickly made it the premier spinblocker in OU, relegating Spiritomb to a life in UU. On top of that, it was a great counter to Scizor, the new "big thing" in OU. Things were looking good for it in Gen 4.
Then Generation 5 opened up, and the rumor mill started chugging. There was a lot of nonsense that was floating around, but at least one thing turned out to be true: the Rotom Formes weren't Ghost-types any more—each took on the type of their respective signature move. This meant that Rotom-W went from Ghost / Electric to Water / Electric, a typing only shared with Lanturn. This gave it an impressive roster of resistances, and also arguably one of the best dual STAB combinations in the game. Combine that with an awesome new move in the form of Volt Switch, and Politoed's Drizzle giving it an accurate Thunder and a powered-up Hydro Pump, Rotom-W quickly became one of the newest stars of Generation 5.
At first glance, there's nothing really outstanding about Rotom-W's stats. 107 / 107 defenses are decent, but 50 base HP doesn't do it any favors. 105 Special Attack is more than competent, but its movepool isn't especially amazing—Electric moves, Ghost moves, and Hydro Pump are basically all it has, but most of the time, that's all it needs. 86 Speed is serviceable, doubly so in this arguably slower Generation 5 metagame.
However, what makes Rotom-W really stand out is its excellent dual typing. Electric / Water is a great typing, with resistances to Steel, Water, Ice, Fire, and Flying, and with Levitate, it also has a crucial Ground immunity. However, even more significant is its meager one weakness—Grass, a type that is rarely carried as a coverage move. To top it all off, it weighs a measly 0.7 pounds, so Grass Knot only hits it for 20 Base Power, making one of the more common Grass-type moves nearly irrelevant. Combine this with decent 50 / 107 / 107 defenses, and even without investment, Rotom-W can give any team a decent check to some top threats in the metagame.
Offensively, it's no slouch either. STAB Hydro Pump and Thunderbolt give Rotom-W great coverage, and Rotom-W's also got a bunch of other useful Electric-type attacks to its name. The new Volt Switch lets it serve as an excellent scout and keep your opponent on the back foot, and it's tough to neutralize it with a Ground-type for fear of getting hit by a STAB Hydro Pump. Discharge lets it spread paralysis if it wants, and if rain is in play, it can use the powerful Thunder to complement its rain-boosted Hydro Pump. It can even play at a boosting set with Charge Beam, though it's not as effective as when it was a Ghost-type in Generation 4.
On the support side, it's no slouch either. Its ghostly heritage grants it access to Will-O-Wisp, making it one of two Water-types with access to Will-O-Wisp (the other being Jellicent), allowing it to cripple physical attackers. It's also got Thunder Wave for reliable paralysis infliction, if Discharge's 30% paralysis and lower Base Power aren't appealing. Pain Split is remarkably effective given Rotom-W's low base HP, since its high defenses let it do more with less HP, while simultaneously dealing damage to the opponent. However, its most notable support move is Trick, which allows it to be an incredible revenge killer with Choice Scarf, yet still use Trick to cripple stall teams (especially those involving Chansey, which is utterly crippled without Eviolite).
Despite not having the most expansive movepool, Rotom-W is actually quite versatile, and it is able to fill many roles in different teams. However, its most notable and arguably most effective set is its Choice Scarf set, which functions as a nightmarish combination of strength, speed, resistances, and scouting capability, similar to Generation 4's Flygon, but on steroids. With a STAB Volt Switch backed by a potentially rain-boosted Hydro Pump and Thunderbolt / Thunder, Rotom-W packs plenty of punch even with only its STABs. On top of that, Trick lets it cripple the walls that would hamper its effectiveness, especially Chansey, Blissey, and Gastrodon. It's a good bet that if you see a Rotom-W on a team, it's this set, and it's going to be leading.
However, Rotom-W actually has higher defenses than offense, and it's more than capable of making use of them. Its mere one weakness (to a not especially common or effective type) combined with Levitate and a bunch of useful resistances make it an excellent defensive pivot. Volt Switch allows it to switch around safely and scout your opponent's movements, and to always keep the defensive momentum up. It can also cripple physical attackers with Will-O-Wisp, and stave off Fire-types hoping to nullify Will-O-Wisp with Hydro Pump. Pain Split rounds things out, as it allows Rotom-W to stay healthy while wearing down opponents.
Rotom-W also has a couple of notable niche sets which are quite effective. Choice Specs allows it to do incredible damage to opposing teams, and is especially effective when the opponent switches in Pokémon expecting a weaker attack from the Choice Scarf set. The other notable set is an Expert Belt set packing Hidden Power Grass. One of the major reasons for Gastrodon's rise to fame is its immunity to Rotom-W's dual STAB, so packing an Expert Belt can allow Rotom-W to lure in its counters and dispatch them with an unexpected move switch. It's especially useful since it can bluff a Choice Scarf set, the most common set seen from Rotom-W.
Rotom-W is such a significant threat in BW that it was almost solely responsible for Gastrodon rocketing directly from NU to OU and staying firmly there for the last couple months. Its combination of Water and Electric immunities makes it the best counter to Rotom-W, which is incapable of damaging it, and can only affect it with Trick or Will-O-Wisp. However, relying on Gastrodon can be iffy, as it can get caught by an Expert Belt-boosted Hidden Power Grass, dispatching it on the spot. This can spell doom if you're lacking in other Rotom-W checks, so make sure Gastrodon isn't your only line of defense against the rogue washing machine.
Beyond that, both Chansey and Blissey are more than capable of stopping Rotom-W's offensive machinations, though as always, Trick is a problem. Defensive variants can also be somewhat troublesome as well, as they can heal up easily off of their gigantic HP with Pain Split. However, they'll never actually be able to defeat Chansey and Blissey, just annoy them. Natural Cure also makes Will-O-Wisp a non-issue, as it can just switch out and nullify it.
Finally, there are plenty of Pokémon that can just take a hit and obliterate it. Virizion resists both of its STABs and can either set up on it with Calm Mind (watch for Trick!) or just kill it with Giga Drain or Leaf Blade. The Lati twins pack the same resistance to both STABs and can blow Rotom-W away with Draco Meteors or other strong Dragon-type attacks. Haxorus resists both, and can even hit Rotom-W with Earthquake thanks to Mold Breaker, but its Special Defense isn't too hot, and Will-O-Wisp utterly cripples it, so be careful. Unfortunately, unlike its Generation 4 incarnation, it can't just get Pursuited away, but you can still just tank a hit and retaliate, or surprise it with an unexpected Choice Scarf set.
Being a Levitate user, Rotom-W doesn't need a lot of support. It's generally pretty easy to fit into any team, but there are still some notable ways to make it even more effective than usual.
The easiest way to optimize Rotom-W's effectiveness is just to keep rain up. Rain not only buffs up Hydro Pump's power, but also allows it to use Thunder with 100% accuracy, making it a major threat with paralysis and giving it a strong accurate STAB move. Additionally, keeping rain up means that sandstorm isn't up, and that makes it easier to keep Rotom-W alive. Additionally, while Rotom-W is immune to Spikes and Toxic Spikes, it still likes to switch in a lot, which means that Stealth Rock can be troublesome, so consider using either a Rapid Spinner or a Magic Bouncer to keep Stealth Rock off the field.
Politoed obviously tops this list, as Drizzle works hard to improve Rotom-W's utility significantly. Beyond that, you'll want a way to deal with Rotom-W's checks and counters if you intend to use it as an optimal member of your team. Pursuit users, especially Scizor, can wear down Chansey and Blissey, as well as the Lati twins, eliminating some of the most notable counters to Rotom-W. Rotom-W also works well with Scizor, as the combination of U-turn and Volt Switch keeps momentum in your favor for a long time. You can also use other Water-types to break down Gastrodon. Stuffing Hidden Power Grass or Toxic on Politoed can do the trick, as few Pokémon want to take a powerful Hydro Pump of Scald from Politoed, so Gastrodon tends to switch into Politoed extremely often.
Despite its radical change in Generation 5, Rotom-W has still managed to keep its title as king of the Rotom Formes in OU, and it's even better now that it's able to differentiate itself. It lends a rare and useful typing with a great stat spread and surgically effective movepool, and it's sure to be sitting pretty in the OU tier for a long time to come. If you haven't tried out Rotom-W in this new generation yet, you owe it to yourself to slap it on one of your teams and observe the magic that happens.
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