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They first kiss under magical influence in "Something Blue"

Then again she kisses him for not telling Glory that Dawn is the Key. THEN the musical episode at the end but she does say/sing that "this isn't real but I just want to feel" before kissing him even in that scene.

Original answer:

Buffy and Spike first kiss at the end of the episode 'Once More With Feeling'. Their relationship from there is complicated and kind of messed up.

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