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I know that you can use all HMs out of battle, but there are some like dig and headbut that you can use out of battle. Does anyone know what all of these moves are and in what games they can be used out of battle?

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Great question! Here are the ones I can think of, there may be more:

  • All the HMs, like you said: Cut, Surf, Fly, Strength, Rock Smash, Rock Climb, Waterfall
  • Defog (HM in Diamond/Pearl/Platinum)
  • Whirlpool (HM in HeartGold and SoulSilver)
  • Flash (was an HM in previous games, it is used to light up dark caves)
  • Dive (HM in Ruby/Sapphire, to allow you to go underwater)

  • Dig (escape from caves)

  • Teleport (warp to last pokemon center, only if outside though)
  • Sweet Scent (attracts pokemon)
  • Headbutt (find pokemon in trees)
  • Softboiled (use Chansey's HP to replenish others' HP)
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Just adding to the HMs, Defog is a Diamond/Pearl/Platinum (for the benifit of anyone else looking at this)
Pokemaster, you are forgetting one. Milk Drink can be used out of battle too.