Let me break it down for you:
Personally I voted too close to call. They both even employ body contact flips easily, Widow against Hammer's bodyguards, Arrow against the assassin who came after him in his house (the flip trick he learned from Yao Fei's battle with Deathstroke). While they both are crazy agile, skilled and throw a barrage of hits at once, there is a key difference.
Widow is precision fight-skill trained, Arrow is not (as far as we know).
The two times we've seen Arrow get taken down easily by a better trained and further experienced combatant, the Dark Archer Merlyn. Merlyn took Ollie down because his training was superior and sought out, it was honed in Nanda Parbat where he went to become the Dark Archer, and this honed skill proved superior to Arrow's asskickery. much like Black Widow.
Black Widow has extensive SHIELD training, pre-SHIELD training, miscellaneous martial arts skills and was a hand to hand combating spy for years. This extensive background much like MERLYN'S,I feel gives her the edge 3 out of 5 times in a battle with Arrow, she could take him down much like Merlyn did. Not to mention she's familiar with Archers and their methods so she could dodge an arrow attack.
BUT and this is an important but, Arrow is a wildcard. We don't know exactly what happened in 5 years to turn him into the weapon he is. He fights like he has nothing to lose, and his official untrained background might give him a slight edge, it makes him unpredictable. Wildcard.
Too close to call.
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