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Smack On means to propose a fight with someone. Generally in a joking manner but can definitely can be used very effectively in a real situation. Smack On is closely associated with the term "punch on".
Joking:
Luke: "You suck apples"
Brad: "Smack on cunt"

Serious:
Josh: "I fucked your ex on a trampoline!"
Ryan: "Smack on cunt!"
by KinnyMcbinspin February 04, 2014
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