Sylar has all sorts of ways to win this. The slayers win fights by punching, their powers are predominantly physical, they're at home in close combat, whereas Sylar has a huge variety of powers, many offensive and ranged, giving him a lot of options here. Sylar has telekinesis, electricity, disintegration, melting, freezing, radiation and anything else else i'm forgetting at his disposal, all of which would be devastating to the slayers, as they can't tank or counter any of those. Sylar's flight and precog mean he's unlikely to get hit and his healing power means any hits landed wont do much, unless the slayers can lodge something in his brain, but without prior knowledge they might not achieve that quickly enough. Sylar could shapeshift into their loved ones as a distraction, but that might not work, and shatter their weapons, not that he'd have to, really.
Both Buffy and Faith have the advantages of martial arts prowess, physical capability and hardcore training and experience, but Sylar doesn't have to go toe-to-toe with them, he can take them both out from afar, so i'm not seeing how they'd win this.
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