The palladium-catalyzed three-component coupling polymerization of p-bromophenylallene and a nucleophile possessing oligo-oxyethylene units was performed to give a poly(p-phenylene-vinylene) derivative having amphiphilic substituents on each vinylene unit in a high yield. The polymer was found to be soluble in organic solvents such as benzene, chloroform, N,N-dimethylformamide, and methanol, whose number-average molecular weight (M-n) and the molecular weight distribution (M-w/M-n) were estimated as 8,600 and 1.76, respectively.