There is a 5% chance that a wild Poliwhirl will be holding one (it is found by fishing with a Good Rod on Route 225, 226, or 228).
Also, Pokemon with the Pickup ability, from levels 11 to 30, have a 1% chance of finding a King's Rock after a battle.
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You have to have a Friend kings rock poliwhirl first put your kings rock on poliwhirl then get A friend to trade and trade back
A wild horsea has a 5% of holding a dragon scale. poliwhirl has a 5% chance of holding a king's rock.
on Pokemon diamond you can only trade whilst holding the kings rock where you get in wayward cave which is under the cycling road
you can find a kings rock on seven island in sevault canyon.
You find the kings rock in the very bottom of the Slowpoke Well (Near the town with the bug Pokemon gym)