Red Mystery Dungeon
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When you gained the ability to go around with only a single team member, you also gained the ability to change which pokémon is the Leader. Remember when Pikachu told you about how you visit a team member in their Friend Area...choose Join Team...and then choose Make Leader? Once you've done that, you can tell the pokémon that was Leader to Stand By. Now the pokémon you want to evolve is alone, and can enter Luminous Cave.
By the way, I hope you're aware that Pikachu needs a Thunder Stone to evolve. You can get those on the 29th floor of the Lightning Field dungeon.
