I remember there being a couple of Mal and Jayne figures released by Diamond Select around the time of the movie. I also remember them being really terrible, sadly.
Robert Tonner made beautiful dolls of Malcolm and Inara. Unfortunately, they were $200 each, and sold out FAST.
He did Doctor Who and Torchwood- Ten and Martha, Jack and Gwen. Again, $200 a pop, and sold out fast.