A series of poly(p-phenylenevinylene) based polymers (MEH-OXD-PPVs) functionalized with Y-shaped double 1,3,4-oxadiazole-containing side chains were synthesized through a modified Gilch reaction. They are all soluble in common organic solvents such as chloroform, tetrahydronfuran and 1,1,2,2-tetrachloroethane. The chemical structures of MEH-OXD-PPVs were determined by ¹H NMR, GPC and elemental analysis. Thermogravimetric analysis shows that they have good thermal stability with the decomposition temperature ranging from 312 °C to 326 °C. The absorption and fluorescence emission maxima of the polymers exhibit an appreciable blue-shift with the increase of oxadiazole-containing moieties. Electrochemical investigation shows that the HOMO energy levels of the polymers vary regularly with the change of content of oxadiazole-containing moieties. Additionally, by introducing more OXD-PV unit during copolymerization, the PL quantum efficiencies of the polymers are significantly enhanced compared to that of MEH-PPV. The successful manipulation of optical and electronic properties of the MEH-OXD-PPVs indicates an effective concept for developing PPV-based functional materials with tunable optoelectronic properties by changing the amount of electron-withdrawing oxadiazole-containing moieties.