Poly(p-phenylene vinylene) (PPV), poly(2,5-dioctyl-p-phenylene vinylene) (PDOPPV), and poly [2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylenel (MEHPPV) were synthesized by a liquid-solid two-phase reaction. The liquid phase was tetrahydrofuran containing 1,4-bis(bromomethyl)benzene, 1,4-bis(chloromethyl)-2,5-dioctylbenzene, or 1,4-bis(chloromethyl)-2-methoxyl-5-(2'-ethylhexyloxy)benzene as the monomer and a certain amount of tetrabutylammonium bromide as a phase-transfer catalyst. The solid phase consisted of potassium hydroxide particles with diameters smaller than 2 mm. The experimental results demonstrated that the reaction conversions of PPV and PDOPPV were fairly high (similar to65%), but the conversion of MEHPPV was only 45%. Moreover, gelation was found in the polymerization processes. As a result, PPV was insoluble and PDOPPV and MEHPPV were partially soluble in the usual organic solvents, such as tetrahydrofuran and chloroform. Soluble PDOPPV and MEHPPV were obtained with chloromethylbenzene or bromomethylbenzene as a retardant regent. The molar mass of soluble PDOPPV was measured to be 2 X 10(4) g mol(-1), and that of MEHPPV was 6 X 10(4) g mol(-1). A thin, compact film of MEHPPV was formed via spin coating, and it emitted a yellow light.