The effect of some metallocenes such as ferrocene (Fe(C5H5)2), nickelocene (Ni(C5H5)2), and cobaltocene (Co(C5H5)2), on the vinyl polymerization initiated with bis(ethyl acetoacetato)-copper(II) (Cu(eacac)2) was investigated. Co(C5H5)2 was found to exert a markedly accelerating effect on the polymerization of methyl methacrylate (MMA) with Cu(eacac)2. The polymerization of MMA with the system Co(C5H5)2/Cu(eacac)2 at 50°C was found to be fairly affected by the solvent used. The results of copolymerization of MMA with styrene (St) and the effect of hydroquinone (HQ) on the polymerization of MMA with Co(C5H5)2/Cu(eacac)2 showed that the polymerization proceeds via a radical mechanism. The polymerization of MMA with Co(C5H5)2/Cu(eacac)2 was studied kinetically in acetone. The overall activation energy of the polymerization was calculated to be 86,3 kJ/mol (20,6 kcal/mol). This value was somewhat higher than that (17,6 kcal/mol) obtained for the polymerization of MMA with Cu(eacac)2 alone. The polymerization rate (Rp) is represented by the following equation: Rp = k[Co(C5H5)2]0,5 [Cu(eacac)2]0,2 [MMA]1,3. The high order in monomer concentration suggests a participation of the monomer in the initiation process of this polymerization. This is supported by the examination of the ESR spectrum of the system Co(C5H5)2/Cu(eacac)2/MMA/acetone, where reduction of Cu(II) to Cu(I) occurs. To elucidate the initiation mechanism, the spin trapping technique was applied to the system Co(C5H5)2/Cu(eacac)2/methyl acrylate. From these results, an initiation mechanism for the binary initiator system Co(C5H5)2/Cu(eacac)2 is proposed and discussed.