Well-defined statistical copolymers of vinyl acetate and 1-(trifluoromethyl)vinyl acetate were synthesized by RAFT/MADIX polymerization. These copolymers exhibited enhanced solubilities in supercritical CO2 compared to poly(vinyl acetate). A copolymer composition-solubility optimum was observed, which resulted from a subtle interplay between polymer-polymer interactions and entropy of mixing.