A polymeric copper complex PS-DCTACE-Cu(II) including cross-linked polystyrene as ligand, whose surface was modified by dicarbonyl tetraza-crown ether groups, was prepared and characterized. It was utilized as a heterogeneous catalyst for methyl methacrylate (MMA) polymerization in Na2SO3 aqueous solution at ambient temperature. The monomer conversion was high and reaction condition was mild. Moreover, the catalyst had good mechanical property and was very easy to be recycled from the reaction system. The polymerization mechanism was also proposed and confirmed by corresponding detections. The polymerization proceeded through a free radical way, in which the radicals were formed by the process of 'chloridion leaving-hydrogen transfer' in this PS-DCTACE-Cu(II)/Na2SO3/MMA System. (c) 2005 Elsevier B.V. All rights reserved.