From Bulbapedia, the community-driven Pokémon encyclopedia.
A Caterpie appeared in ''[[XY001|Kalos, Where Dreams and Adventures Begin!]]''.
A Caterpie appeared in ''[[XY002|Lumiose City Pursuit!]]'', ''[[XY010|Mega-Mega Meowth Madness!]]'', ''[[XY040|Day Three Blockbusters!]]'', and ''[[XY137|Battling With a Clean Slate!]]'' at
[[Professor Sycamore ]]'s lab.
A Caterpie appeared in a flashback in ''[[XY121|Seeing the Forest for the Trees!]]''.