We have investigated the optical properties of a series of poly(p-phenylene vinylene) (PPV) copolymers. Three-wide bandgap PPV copolymers were synthesized and characterized. The new PPV copolymers showed a large blue shift in both absorption and emission that their average bandgap is over 3.1 eV. A significant solvatochromic effect was observed in the photoluminescence (PL) spectra of copolymers. The dimethoxy-substituted copolymer showed the highest quantum efficiency and processability among three copolymers.