The spontaneous copolymerization of 4-vinylpyridine (4-VP) complexed with three different zinc salts (chloride, acetate, and triflate) with various electron-rich vinyl monomers (p-methoxystyrene, MeOSt; p-methylstyrene, MeSt; alpha-methylstyrene, alpha-MeSt; p-tert-butylstyrene, BuSt; styrene, St) was investigated in methanol at 75 degrees C. Increasing the zinc salt concentration or the nucleophilicity of the electron-rich monomer increased the copolymer yields. All obtained copolymers are characterized by high molecular weight (10(5)) and broad molecular weight distribution. Both H-1-NMR and elemental analyses confirmed the almost 1 : 1 copolymer structure. Changing the anion of the zinc salt does not have a considerable effect either on the copolymerization rate or on the molecular weight. The proposed mechanism exhibits the formation of a sigma-bond between the beta-carbons of the two donor-acceptor monomers. This creates the 1,4-tetramethylene biradical intermediate which can initiate the copolymerization reaction.