A novel poly(p-phenylenevinylene) PPV-based copolymer (3C-OXD-PPV) with electron-deficient oxadiazole segments as the side chain has been successfully synthesized through the Gilch polymerization. The obtained copolymer is soluble in common organic solvents such as chloroform, tetrahydronfuran, and 1,1,2,2-tetrachloroethane. The copolymer was characterized by H-1 NMR, elemental analysis and GPC. TGA measurement of the copolymer shows it has good thermal stability with decomposition temperature higher than 350 degrees C. The absorption, electrochemical properties of the 3C-OXD-PPV were investigated and also compared with the properties of MEH-PPV. The HOMO and LUMO levels of 3C-OXD-PPV were estimated from the electrochemical cyclic voltammograms. Bulk-heterojunction PVCs were fabricated by using 3C-OXD-PPV blended PCBM as an active layer. The PCE of the PVC is 1.60% under 100 mW cm(-2) AM 1.5 illumination, which indicates that 3C-OXD-PPV is a potential candidate for the application of polymer PVC. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1003-1012, 2009