PokéBase - Pokémon Q&A
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I’m pretty sure that for every Pokémon except your starter in LGPE, walking and interacting with your Pokémon raises its affection level.
Raising its affection level by more than usual or...
Affection is different from friendship.
In other games, you gain affection by petting your Pokémon in Poke amie / Pokémon refresh, which can then grant you bonuses in battle, like increased chances to dodge/crit, the ability for a Pokémon to overcome status problems between turns, etc. But in Let's Go, you can only pet your starter, so I'm pretty sure that for other Pokémon, affection is raised by walking and talking to them.

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