The Pokémon that can learn Sleep moves are Darkrai, Sunkern, Sunflora, Roselia, Snover, Abomasnow, Leafeon, Shaymin, Poliwag, Poliwhirl, Poliwrath, Politoed, Gastly, Haunter, Gengar, Drowzee, Hypno, Exeggcute, Exeggutor, Hoothoot, Noctowl, Yanma, Stantler, Ralts, Kirlia, Gardevoir, Spinda, Lunatone, Glameow, Purugly, Bronzor, Bronzong, Spiritomb, Smoochum, Jynx, Cleffa, Clefairy, Clefable, Igglybuff, Jigglypuff, Wigglytuff, Chansey, Blissey, Lapras, Skitty, Delcatty, Swablu, Altaria, Kricketune, Chatot, Paras, Parasect, Shroomish, Slowpoke, Slowbro, Slowking, Snorlax, Togepi, Togetic, Wooper, Quagsire, Dunsparce, Slugma, Magcargo, Kingdra, Slakoth, Slaking, Gulpin, Swalot, Chimecho, Relicanth, Bidoof, Bibarel, Hippopotas, Hippowdon and Uxie.
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No Pokemon can learn more than four moves.
There are no items that can put Pokemon to sleep, only moves like hypnosis and sleep powder.
Dark hole, hypnosis, yawn, sleep powder.
some Pokemon do learn some don't
Venusaur Learns:- Growth Lv.43 Sleep Powder Lv.55 Solar Beam Lv.65