Polymer-metal complexes (PMC) catalyst was synthesized by cross-linked polyvinylamine (PVAm) with Cu(II). It has been found that PVAm-Cu(II)/sodium sulphite (Na2SO3) system can use as initiator for polymerization of methyl methacrylate (MMA). The overall polymerization rate can be expressed as R-p = k[MMA](1,4)[Na2SO3](0.5)[PVAm-Cu(II)](0). E-a = 61.3 KJ mol(-1). The influences on conversion of polymerization and molecular weight of polymerization of MMA have been investigated with compared to that of polymerization initiated by Cu2+/Na2SO3 system. Mw of PMMA initiated by PVAm-Cu(II)/Na2SO3 system can reach 1240000. It has been observed that the influences of constitute of PVAm-Cu(II) have impact on the activity in polymerization of MMA. The polymerization is preceded by free radical, and primary radicals are formed by the process of "complexation-hydron transformation" between PVAm-Cu(II)/Na2SO3/MMA system. (C) 2003 Elsevier B.V. All rights reserved.