A new type of homogeneous catalyst for dimethyl carbonate (DMC) synthesis by oxidative carbonylation of methanol in the liquid-phase reaction was investigated. The polymer-bound monometallic PVP-CuCl2 catalyst (PVP, poly (N-vinyl-2-pyrrolidone)) prepared by the combination of an alcoholic solutions of PVP and CuCl2 exhibits excellent catalytic performance for the oxidative carbonylation of methanol with carbon monoxide and oxygen to DMC under 3.0 MPa (P-O2 = 0.24 MPa and P-CO = 2.76 MPa) pressure at temperature around 140-160 degreesC. The catalyst exhibits much higher activity and selectivity than non-supported CuCl, in the DMC synthesis reaction. The remarkable increase in the conversion and selectivity is attributed to the presence of a strong complexation effect between Cu(II) and the amide ligands in the polymer chains. (C) 2002 Elsevier Science B.V. All rights reserved.