Arylene-vinylene-containing polymers with fully aromatic backbone structures were prepared by the palladium-catalyzed hydroarylation polymerization of diethynylbenzene derivatives with diiodobenzene and alkylmalonate anions as a hydride source. For instance, the polymerization of 1,4-bis(4'-dodecyloxy)phenylethynylenebenzene, diiodobenzene, and sodium diethyl benzylmalonate was carried out at 80 degrees C for 2 days in 1,4-dioxane in the presence of Pd(OAc)(2)/tri-o-tolylphosphine (7 equiv. to Pd) to produce a polymer (M-n = 6,390, M-w/M-n = 1.53) in high yield (86 %). Using various diethynylbenzene derivatives, polymers having arylene-vinylene units were also obtained in high yields.