The Bright Sessions is a Radio Drama absolutely full of Superpower deconstructions and justifications, and manages to make an empath empathetic. It's based around a Psychologist who sees these people with superpowers (and who is not an empath) and they really make the most of a simple format.
Treknologic is an amazing podcast. The hosts have an innate ability to be funny and serious at the same time, and are actually accepting of ideas different from their own. This, along with a strong fanbase and fun trivia, begs one to ask why the show isn't more popular.
Six Feats Under is an actual play podcast focused on tabletop RPG's beyond Dungeons & Dragons. It has a high production quality, a rotating cast of engaging players, and both of its currently ongoing campaigns are filled with complex, unique characters and compelling, inventive, and lived-in-feeling worlds.
Old Harry's Game is a British Radio Drama about Satan and his demons tormenting two new arrivals in Hell: a CEO who is so awful Satan himself is disgusted by his morals, and a professor who only ended up in Hell for atheism and believes he is hallucinating his afterlife. Hilarious, well-written and well-acted; Andy Hamilton is perfect as head writer and as the voice of the Devil.