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In this work, we report the hybrid copolymerization of various cyclic monomers and vinyl monomers.Our studies demonstrate that 1-tert-butyl-4,4,4-tris-(dimethylamino) -2,2-bis[tris(dimethylamino) phophoranyliden-amino]-2A5,A5-catenadi(phosphazene) (t-BuP4) can catalyze the hybrid copolymerization of caprolactone (CL), lactide (LA), cyclic carbonate ester or ethylene oxide (EO) with acrylate or methyl acrylate.However, the polymerization of cyclosiloxane with vinyl monomers yields two corresponding homopolymers, the polymerization of lactone with acrylonitrile (AN) produces only polyacrylonitrile and the polymerization of propylene oxide (PO) with methyl acrylates yields only the poly(methyl acrylate).Clearly, the matching of activity between a monomer and an active center determines the hybrid copolymerization.