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All Electric-type attacks, even those from your ally in 2v2, hit this Pokémon with 100% accuracy, regardless of the intended target. If a Pokemon with Lightningrod and a Pokemon using Follow Me are out at the same time, and a Pokemon uses an Electric-type attack targeted at the Follow Me user's team, Lightningrod will still take precedence and absorb the attack. Lightningrod never attracts Hidden Power, even if Hidden Power is Electric.
When a Pokémon with Lightningrod is present in your party in Emerald, the chance of you receiving an Entry Call on the Pokénav is increased.