Pikachu has Thundershock and growl when you first get it at a low level. Then it learns: Tail whip at level 5 Thunder wave at level 10 Quick Attack at level 13 Double Team at level 18 Slam at level 21 Thunderbolt at level 26 Feint at level 29 Agility at level 34 Discharge at level 37 Light Screen at level 42 Then Thunder at level 45 It can also learn alot of TM's aswell.
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It learns Harden at level 7, and that's it.
Whenever you want. Bare in mind that Raichu won't learn any new moves as you level it up, so just make sure your Pikachu has all the moves (that it learns via leveling up) you want it to before you evolve it.
Lv. Move 23 Body Slam 43 Earth Power 58 Superpower
Pikachu can only learn volt tackle if you have a ditto in the day care and you catch a pikachu with a light ball in its possesion. Then you have to bring the pikachu to the day care and hatch the egg, then your new pichu will learn volt tackle!!!!!!!!Pikachu Learns ThunderBolt at level 26 (95 Pwr)(15 PP)
What you do is trade pikachu with a red or blue game then once he is traded evolve him with a thunderstone than trade him back. But be warned once you do that you can't walk with him or talk to him. And he can't learn new moves. It baically runes the whole story line so I wouldn't bother evoving him at all.