This paper is concerned with charge transfer complex properties of copolymers with pendant electron-donor and electron-acceptor groups obtained by radical copolymerization. The complexing groups were carbazolyl, anthryl, phenothiazinyl, and p-dimethyl-aminobenzyl as electron-donor groups, and picryl, dinitrophenyl, dinitrobenzoyl, and trinitrofluorenyl as electron-acceptor groups. The microstructure of such copolymers, including the tendency to alternating and coisotactic addition, together with the influence of monomer structure and reaction conditions, is discussed. Intramolecular complexation interactions are analyzed. These properties were measured by means of1H-NMR and electronic absorption spectra. Finally, some physical properties, e.g., color, solubility, density, and photoconductivity, are presented to illustrate the intramolecular and intermolecular complexation interactions. It is concluded that such copolymers are weak charge transfer complexes of the π-π type. They are of theoretical interest for study of the correlation between synthesis, structure, and properties, and of practical interest due to their optoelectric properties.