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In short, how do you do it and is it worth fully upgrading? It sounds useful (and cool) and I can certainly imagine archers being a pain in the ass, especially if they "twitch" Geralt out of his block stance. On the other hand, I've played enough RPGs to know that sometimes the skills that sound cool are actually crappy for one reason or another, or that there might simply be hardly any archers in the game (kind of like learning anti-undead skills in an RPG where the undead are in it for only one small part).
This question / problem has been solved by Borlagimage
You use it by blocking, which then redirects the arrow. In my opinion the skill is rather useless, as there simply isn't enough archers in the game to warrant wasting a point in protecting against them. Rather spend that point in other forms of protection.