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In Cerulean, there is a old man who wishes to trade a Poliwhirl for a Jynx. After trading, (you will have needed to have beaten the Elite 4 and have gotten the Rainbow pass from Oak) travel to Four Island and breed Jynx with a ditto (route 15 & cerulean cave) and whala. Smoochum.
Breed Jynx with Ditto at the four island daycare hatch the egg to get smoochum.

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