The specific features of free-radical polymerization of methyl methacrylate in the presence of a new initiating system, benzoyl peroxide-N,N-dimethyl-N-(methylferrocenyl)amine, are studied. Mutual influence of ferrocenyl- and amine groups on kinetic parameters of polymerization and on the microstructure of the resulting polymers is found. It is shown that the polymer obtained in the presence of this initiating system has predominantly syndiotactic structure. (c) 2006 Wiley Periodicals, Inc.