The present review is an attempt to generalize and systematize the results accumulated in complex-radical copolymerization, as well as to analyze new aspects of alternating copolymerization of functional-substituted ehtylenes as acceptor monomers with various electron-donor monomers having different types of conjugation between double bond and functional groups. The classification of mono- and bifunctional monomers is described from position of their acceptor-donor properties depending on the type of conjugation of double bond and functional groups. Phenomenon of monomer charge transfer complex (CTC) formation in radical copolymerization, cyclocopolymerization and terpolymerization reactions and its effect on kinetics and mechanisms of formation of copolymers with alternating structure are discussed in detail. In this review, new aspects of complex-radical copolymerization such as coordination effect in radical copolymerization of organotin monomers, effects of monomer CTCs, keto-enol tautomerism and cis-trans isomerism in the formation reactions of functional macromolecules with given structure and properties are described. (C) 2000 Elsevier Science Ltd. All rights reserved.