Abstract
An electroactive polymeric surfactant with pendent long‐chain viologen redox groups, 
, was synthesized by the reaction of poly(chloromethylstyrene) with N‐hexadecyl‐4(4'‐pyridyl)pyridinium bromide. Films of this polymeric‐surfactant on glassy carbon electrodes were studied by electrochemical, microscopic, spectroscopic (absorption‐probe), and electron spin resonance techniques. The results suggest that upon reduction of the viologen groups in aqueous solution, the structure of the polymeric surfactant becomes more compact, probably because of reorganization induced by a decrease in the coulombic repulsive interaction. Spherical domains formed by the aggregation of the long‐chain hydrocarbon groups were observed in the transmission electron micrographs of both the oxidized form and reduced form of the polymeric surfactants.