In A Rivalry to Gible On!, Totodile was used to help track down a wildGible that was attacking people near a Pokémon Center. After getting into a scuffle with Buizel, Totodile and its Trainer were eventually able to find Gible. Totodile matched Gible's moves, wearing it down allowing Khoury to catch it.
When Pikachu and Piplup first introduced themselves to Totodile, it ignored them. However, it appears that the only reason Totodile was being unsociable was because it was upset that it had been given food it did not like. It was later seen being friendly with the other Pokémon.
As a reflection of its Trainer, Totodile seems to care for Lyra as a friend, prompting her to get on stage at the festival and alerting her and the others that her Marill had wandered off. It also seems to be quite the competitive Pokémon, evidenced by its quarreling with Buizel and fighting an unorthodox battle with Gible. In contrast to Ash's Totodile, it is not as energetic.