The March of the Exeggutor Squad - S1-E41
Other mistake: The Pokemon Exeggcute is shown evolving in to an Exeggutor naturally. But the Pokemon Exeggcute can only evolve into an Exeggutor with the use of a leaf stone. In the Japanese version, there is a mention that something in these woods causes Exeggcute to evolve without using the Leaf Stone (when Exeggcute evolves, James even mentions that there is no stone). However, as this was skipped in the English version, it creates a plot hole.
Answer: He is a good guy but just found himself in a bad situation when he worked for Lysander. He didn't want him to harm Ash and his Pokémon when he was trying to get the special bond between Ash and his Greninja to work. He does leave Lysander and go back to being a good person.