Eldritch Blast regularly misses to me, even on high % hit chance, this happens ALL THE TIME, NOT JUST SOMETIMES! And it goes the other way around, too, I can send Karlach in with confidence of her hitting at least one of the two hits, mostly both, if I send her with a reckless attack+great weapon master at something with a 34% hit chance.
All I can say, is that's not been my experience. I definitely haven't noticed discrepency between one skill and another, and in general things seem to hit about as often as I would expect. I ha some unlucky streaks, but I also had some lucky ones.