Two new poly(p-phenylenevinylene) (PPV) derivatives containing the oxadiazole moiety (OXA-PPV1 and OXA-PPV2) were synthesized by the Wittig condensation polymerization reaction and their thermal and light-emitting properties were investigated. The single-layer and triple-layer electroluminescent (EL) devices with configurations of ITO/OXA-PPV1/Al and ITO/OXA-PPV1/OXD/Alq(3)/Al were fabricated. They both exhibited blue emission at 460 nm. For comparison, the PPV derivative containing the oxadiazole moiety only in the side chains (OXA-PPV2) was also synthesized. Both single-layer and triple-layer EL devices with OXA-PPV2 as the emissive layer emitted green-light at 560 nm. The turn-on voltages of the triple-layer device was 11 V for OXA-PPV1 and 8 V for OXA-PPV2. The triple-layer EL devices showed much better performance than that of the single-layer devices. The spectra indicated that energy or electron transfer occurred from the side-chain oxadiazole to the main-chain styrene unit.