The polymer-supported bimetallic catalyst system PVP-PdCl2-CuCl2/PPh3 has good conversion and regioselectivity to carbonylation of alpha-(6'-methoxy-21-naphthyl)ethanol under mild conditions. The effects of temperature, CO pressure, reaction time and P/Pd ratio have been studied to obtain optimum reaction conditions. The carbonylation of various alpha -arylethanols and styrene derivatives are also investigated with the same catalyst. X-ray photoelectron spectroscopy (XPS) and transmission electron micrograph (TEM) show that the polymer would protect palladium particles against aggregation and serve as a ligand.