A novel oxadiazole-based copolymer has been successfully synthesized through the palladium-catalyzed cross-coupling polycondensation method. The copolymer P is soluble in common organic solvents. Its structure has characterized by 1H NMR, 13C NMR, gel permeation chromatagraphy (GPC), UV-vis absorbance (Abs) and photoluniminescence (PL) spectroscopy, and cyclic voltammetry (CV). Investigation of its optical properties revealed that it is yellow emitting material, and the electrochemical analysis showed that P was well suited poly (2,5-dioctyloxy-p-phenylenevinylene) (PDOCPV) for photovoltaic devices, so the copolymer P is able to act as an electron acceptor in combination with PDOCPVas the electron donor to quench photoluminescence of the copolymer in the blend, indicative of the efficient photoinduced electron transfer from the PDOCPV to the P.