A novel synthetic method for soluble precursor polymers of poly(p-phenylene vinylene) (PPV) derivatives by the palladium-catalyzed three-component coupling polycondensation of aromatic diiodides, aromatic bis(boronic acid) derivatives, and norbornadiene is described. For example, the polymerization of 1,4-diiodo-2,5-dioctyloxybenzene, benzene-1,4-bis(boronic acid propanediol ester), and norbornadiene at 100 degrees C for 3 days provided a polymer consisting of the three monomer units in a 97% yield (number-average molecular weight = 3100, weight-average molecular weight/ number-average molecular weight = 1.37). A derivative of PPV was produced smoothly by the retro Diels-Alder reaction of the polymer both in a dodecyloxybenzene solution and in a film at 200 degrees C in vacuo. (c) 2005 Wiley Periodicals, Inc.