Zoro likes being with Luffy, follow his orders and would abandon his won dream for his captain so no he is not gonna ever be a villain and about Luffy fighting Zoro in this imaginary scenario(which probably is your point of this thread) so then yes obviously Luffy can defeat him.
While it would be HILARIOUS for the “Pirate Hunter” to immediately betray the new King of Pirates, a) Oda does not currently possess the kind of balls required to pull that off, nor has he ever, b) this is really the only time anyone has reinforced their commitment to the crew (a proclamation following AND in discussion about one of two members who had just left the SHP), would be a stunning and highly out of character move for him to suddenly turn on everyone he loves:
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