Abstract: After had been soakod with cupric ammine aqueous solution, the film of PVA was measured by ESR, water solubility test, differential thermoanalysis and thermogravimetry, XPS,IR, experiment of electrophoresis-helium and neon laser beam, scanning electron microscope and high efficient liquid chromatography. This paper make synthetically and investigation on the interaction between PVA with Cupric（Ⅱ） ion, structure of its product and catalytic activity of above film. The system of Cupric （Ⅱ）-PVA coordination polymer with Na₂SO₃ can catalyze MMA to initiate polymerization in water phase at room temperature. The yield of PMMA is more than or egual to 50%, M_∞=35.33×10⁴,M_n=8.5×10⁴,the dispersity of distribution for molecular weight is 4.16.