Challenge of the Samurai

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Debuts

 * Weedle (Ash's)
 * Pinsir
 * Kakuna

Major events

 * Ash catches a Weedle.
 * Ash learns that a Trainer can only have six Pokémon on hand at once, and that his extras are automatically sent to reside at Professor Oak's Laboratory.
 * Ash has his first fair Trainer battle, with no official winner.
 * Ash's Pidgeotto is revealed to know Sand Attack.
 * Ash's Metapod is revealed to have learned Harden.
 * Meowth is revealed to know Scratch.
 * Ash's Metapod evolves into Butterfree and learns Sleep Powder.

Humans

 * Ash
 * Misty
 * Jessie
 * James
 * Samurai

Pokémon

 * Pikachu (Ash's)
 * Meowth (Team Rocket's)
 * Pidgeotto (Ash's)
 * Metapod (Ash's; evolves)
 * Butterfree (Ash's; newly evolved)
 * Weedle (Ash's; new; debut)
 * Squirtle (Gary's; flashback)
 * Pinsir (Samurai's; debut)
 * Metapod (Samurai's)
 * Bulbasaur (Trainer's; flashback)
 * Charmander (Trainer's; flashback)
 * Weedle (multiple; debut)
 * Kakuna (multiple; evolve; debut)
 * Beedrill (multiple; some newly evolved)