Who's This? The Switcheroo Witcheroo!
How you could have heard of her: The Enchantress appears in Legends of Tomorrow, but the actual live action appearance people will remember is in the Oscar-winning Suicide Squad movie, as played by Cara Delevigne (she is destroyed and June Moon is freed). In animation, she appears in both DC Super Hero Girls and Harley Quinn (where she is dating Killer Croc).
Example story: Strange Adventures #191 (August 1966), "Beauty vs. the Beast" by Bob haney and Howard Purcell
Her stories were silly, sure, but so was a lot of DC's output and it didn't stop those series from taking off. In this case, I think maybe Zatanna, introduced 2 years ealier, became THE sorceress hero and sank June Moon's chances at the big time. It's still a leap to go from almost-ran to villainess by her 4th appearance, but it seems to have given her some legs. It would prime her for a redemption arc and a shot at being a hero in the same team as, looky here, Zatanna. Sisterhood!
Who's Next? Male and female Firestorm villains.