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Which NPC Pokémon battles have been your most enjoyable or most challenging experiences?

The Totem Battles in Sun/Moon/US/UM were all pretty impressive. None of them were absolute walls, of course, but they were the first attempt to make "unfair" fights and I think they hold up as an interesting way of doing that.

For more traditional, I will always remember my first time in XY, wandering through an early-game route, and hitting double Furfrou. Yes there's harder battles, but that one combines the player has very few tools with double battles, OP for that point in the game mons, and "who would bother to save before this". Just a very scary fight out of nowhere.
 
The Totem Battles in Sun/Moon/US/UM were all pretty impressive. None of them were absolute walls, of course, but they were the first attempt to make "unfair" fights and I think they hold up as an interesting way of doing that.

For more traditional, I will always remember my first time in XY, wandering through an early-game route, and hitting double Furfrou. Yes there's harder battles, but that one combines the player has very few tools with double battles, OP for that point in the game mons, and "who would bother to save before this". Just a very scary fight out of nowhere.
I don't remember the double Furfrou fight, as it's been a while since I played XY, but the totem battles were a lot of fun. Well-designed, clever battles.

If it counts, the battle CDs in Pokémon XD were very fun. They felt like clever little puzzles. I wish this was a recurring feature in Pokémon games.
 
I don't remember the double Furfrou fight, as it's been a while since I played XY
The double furfrou battle itself was nothing special, it was just a double battle vs two furfrous outside Parfum Palace.

The reason most people remind it is cause Furfrou with its Fur Coat is actually a pretty scary pokemon that early in the game, and being a normal type only weak to fighting which again is... mainly physical... means it's easy to actually have your team nuked by them.

Even just looking "double furfrou battle" on google will be followed by a bunch of terrified reddit posts.
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I don't remember the double Furfrou fight, as it's been a while since I played XY, but the totem battles were a lot of fun. Well-designed, clever battles.

If it counts, the battle CDs in Pokémon XD were very fun. They felt like clever little puzzles. I wish this was a recurring feature in Pokémon games.

Ah, that "make six Pokemon faint in a single turn" battle is the best without a doubt
 
As someone who’s played (almost) every main series game at least once and has actually completed the main story of every generation since 3 at least once, it’s very hard to impress me with an NPC Pokémon battle, in large part because the games are so easy on account of being made for players of all ages- which for all intents and purposes means these are kids games. Kids games are fun to go back to for nostalgia purposes from time to time, but rarely do these more accessible games have the same level of complexity that’s easier to appreciate as, in my case, a young adult.

I mention all of this because, for me, the difference between a good Pokémon battle and a great Pokémon battle is all within the buildup to the fight. The story writing, the implications left by the characters, how difficult it actually is to reach the battle in question; these are all factors that can make a fight more memorable if handled correctly. Well designed battles have a tendency to also be some of the most enjoyable and/or fun, and if I had to pick one battle from the core series games that does this the best… I’m going to be honest, I’m not sure I could. Simply because none of them have impressed me enough. That isn’t to say that some battles aren’t harder than others, of course. Gym Leaders that specialize in tricky Types to deal with in their respective games for their point in the game come to mind, but even then most main story battles throughout the entire core series don’t make use of stuff like EVs and competitive movesets. The one time that comes to mind when they did do this is unfortunately attached to the rest of BDSP being stupidly easy up to that point, though I suppose it beats Platinum’s Elite Four having no competitive movesets and lower levels at the same time.

But what about the spin-offs? In a sadly far too common case of “slept on spin-off titles do things better than the main series” (this isn’t just a Pokémon problem), there’s quite a few major battles I can think of that have left an impression on me. On the “standard RPG style” side of things, we have Evice from Pokémon Colloseum, a fight that gets a lot of slack because of the brutal difficulty curve but when me and a close friend tried to beat him for the first time not too long ago, I found that navigating this fight felt less like an unfair difficulty spike and more like a fun puzzle to complete. What strategies with Colloseum’s limited options were the best fit? What ways could we use to try and bridge that level gap with as little extra grinding as possible? By comparison, this isn’t like, say, the postgame of Black & White 1 where your team is in the low 50s and all these Trainers have stacked teams in the 60s or higher, or the battle with Red in the Johto games where the difficulty jump is arguably a bit too large, especially in Gen 2 with limited grinding options for that late in the game.

On the “action spin-off” side of things is where things get really interesting, though. The boss fights of the Pokémon Ranger games tend to be elevated by the surprisingly memorable characters who are sending these Pokémon out for you to calm down, and some of these across the trilogy can actually be deceptively challenging to go along with it. I would hardly consider these action games as much as something like Ranger, but some boss fights in the Pokémon Rumble games also come to mind, more specifically the Cobalion battles in the 2011 3DS installment Rumble Blast. You actually fight this Cobalion twice in the game, and the first fight is a very rare instance of a forced loss battle in an officially licensed Pokémon title, which combined with the unironic surprisingly deep lore of a game about chibi toy Pokémon creates a much welcomed desire for the player to continue playing and eventually come out on top later in the game’s main story.
Yeah, so remember this post? Since writing that, I did actually remember a few main story battles that come to mind. Unfortunately outside of maybe Norman and one of Johto’s rival fights, none of these are Gym Leaders, Elite Four, or any other required story battles remain particularly memorable to me like I mentioned in my original post here. That being said- some of the better battles often lie off the main path, perhaps rewarding players for exploration. Others may be on the main path but be mixed in with other, lesser fights. Regardless, here’s some more I can… vaguely remember, at least.
  • I can’t remember exactly where she is- I want to say Route 120 but don’t quote me on that- there’s an Ace Trainer with a Milotic way before the Gym battle against Wallace. Admittedly I am going off of only ORAS here; I can’t remember if she’s in Gen 3 Hoenn too. Unfortunately she only has just the Milotic, otherwise more people would probably mention her.
  • The two Gym trainers before the first Gym battle in Black & White 1 can be deceptively tricky. They’re not likely to sweep your team or anything, but since level grinding around Straiaton City is very limited outside of Trainer battles, you pretty much have to use your starter here, and in that Level 10-14 range you’ll be at, STAB 50 BP Tackle (remember, this is Gen 5) is actually pretty strong.
  • There’s a Poké Maniac in Mt. Mortar in Gen 2 that has a Nidoking and a Nidoqueen at Level 17. They might also be in Gen 4 Johto, similar to what I said about the Milotic Ace Trainer, but nonetheless the funny part remains the same- a second optional Trainer located after this one towards Mahogany Town only has a Level 16 Nidorino and Nidorina. I didn’t know about this until I started playing Crystal lately on the Virtual Console version and I just found it funny how they were seemingly out of order.
  • Literally the very first NPC Trainer in Sinnoh. No, I’m not joking. Youngster Tristan has a Level 5 Starly in all versions of Sinnoh, which in turn means STAB 40 BP Quick Attack. Again, far from impossible, but the earlygame disparity between Quick Attack Starly and everything else is noticeable in a region full of the less reliable Tackle. It also has Growl to lower your own Pokémon’s Attack for good measure, and can be a challenge for a Level 6-7 Chimchar or Piplup (Turtwig has Withdraw so it should be fine).
 
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