In cartoons, female villains are often played as sympathetic (and possible love interests for heroes). Or, they may have some character weakness that makes them less effective. (Like the Baroness and her Jealousy.)
And then there's Madame Rouge, who seems to be 100% evil and loving it.
But watching again, I see they weren't meant to be sympathetic like other villains in the show. They're evil. (It's right there in the name.)
For Madame Rouge, who I keep wanting to call Madame Rogue, I used a Chameleon Girl Heroclix and tried to fashion Rouge's hairstyle with limited success.
I think the pose on this mini really sells it.