He was voiced by famous voice actor Marc Thompson.
When Ash and his friends found a piece of one of Rico's traps in the woods, they told Officer Jenny about it when they visited the Pokémon Center. Jenny knew Rico was up to his usual evil deeds, and Ash and his friends volunteered to help Jenny capture Rico. Ash and his friends didn't find Rico, but Jessie, James and Meowth found him, along with a group of caged Ekans and Koffing which Rico was going to give to his employers. Team Rocket fought Rico for the freedom of the Ekans and Koffing, but Rico defeated them, although Team Rocket managed to rescue the Ekans and Koffing. To be sure they were safe, they released their Arbok and Weezing to look after them.
After running into Ash and his friends and Officer Jenny he ended up being captured. As Rico confessed to Ash and his friends and Jenny that the Pokémon he captured escaped, they were unaware of the fact Jessie, James and Meowth freed them. He is currently in jail.