A new kind of copolymerization between styrene and p-quinodimethane intermediates was realized by adding styrene to a reaction performed via the typical chlorine precursor route toward ther synthesis of poly(p-phenylene vinylene) (PPV). The composition and structure of the obtained copolymers an be adjusted by the feed rate of the two monomers. The resulting copolymers show improved solubility and blue-sifted photoluminescence as compared with the corresponding PPV derivative.