Novel class of p-phenylenevinylene copolymer with sulfonylene group in the main chain (PPVS) was synthesized through the Wittig reaction of bis(bromomethyl-p-phenyl)sulfone triphenylphosphonium salt with terephthaldehyde. PPVS was highly soluble in common organic solvents and showed strong blue-shifted fluorescence because the polar sulfonylene group provided better solubility and limited pi-conjugation in polymer chain. A single layer device with PPVS sandwiched between indium-tin-oxide (ITO) and aluminum electrodes showed a blue electroluminescence (EL) peaked at 470 nm under the threshold voltage of 14 V. HOMO and LUMO levels of PPVS were found to be 0.46 and 0.28 eV, respectively, lower than those of poly(p-phenylenevinylene) (PPV).