Vinyl polymerization initiated by a copper complex immobilized on a novel polymer and characterization has been studied. Monomer, 4-aldehyde-3-hydroxy phenyl acrylate (Ahpa), and its homopolymer, poly(4-aldehyde-3-hydroxy phenyl acrylate) (PAhpa), were synthesized and characterized using IR, elemental analysis, H-1 NMR, TOF MS, etc. The side chain of the polymer can further coordinate with transition metal ions. Its polymeric Cu(II) complex in Na2SO3 system is proved to be another useful catalyst in polymerization of methyl methacrylate (MMA) at room temperature. The obtained poly(methyl methacrylate) (PMMA) is similar to those determined by conventional free radical polymerization at the same conditions. Moreover, the catalytic mechanism studied was a "Coordination Hydrogen-Transfer" process, which is different from that of CuCl2/Na2SO3 system, but analogous with that of PVAmCu(II)/Na2SO3 (PVAm=polyvinylamine) system, was speculated and testified. (c) 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104:1285-1290, 2007.