Novel triphenylamine- and oxadiazole-substituted poly(1,4-phenylenevinylene)s (PPV) or CN-PPV (P1-4) were synthesized by the Wittig-Horner, Knoevenagel, and Gilch type polymerization. The polymers exhibited good solubility in common organic solvents, relatively high photoluminescent (PL) efficiency, and high HOMO level for ca. -5.1eV. The simple double-layer devices of triphenylamine-PPV (P1), ITO/PEDOT: PSS/P1/Cs/Al, exhibited a very high luminance of 510cd/m 2 under a low driving voltage of 3V, demonstrating the effectiveness of triphenylamine moiety as a substituent of PPV derivatives for a light-emitting polymer. Triphenylamine-CN-PPV (P2) exhibited bipolar reversible redox in CV. The bipolar type of PPVs, P2 and triphenylamine-oxadiazole-PPV (P3), showed lower luminance and efficiency than those of the p-type of PPV (P1).