Re: Black Widow or Madame Masque???
^I'd say both Marvel and DC. The last decent female villain we had that wasn't portrayed in a somewhat simpathetic light was Ursa in Superman 2. Mystique was part of the evil mutants(who were simpathetic since they were fighting against their own oppression) and Catwoman was more of an anti-hero.
Current comic book TV show grades(ones that I watch, at least): Agents of Shield-[season 1: B-][season 2: B+]\The Flash-[season 1: B+/A-]\Arrow-[season 1: B+][season 2: B][season 3: C]\Agent Carter-[season 1: A-]\Daredevil-[season 1: A+]\iZombie-[season 1: A-]