General methods are described for the synthesis of electroactive polymers and the preparation of uniform, stable, polymer-coated electrodes. The electrochemical behaviour of thin films of eight different functionalized polystyrenes, differing in the identity and amount of attached electroactive species, and polyvinylferrocene is presented. A wide range of electrochemical properties can be observed by varying parameters such as film thickness, nature of the bound redox couple, extent of polymer functionalization and oxidation state. The deviations from ideal surface behavior are investigated in detail. These are shown to be consequences of cooperative electronic interactions, structural reorganization or uncompensated resistance within the film, depending upon the material. The film resistance varies greatly among the polymer films studied and is shown, in some cases, to be a sensitive function of the extent of oxidation and prior treatment of the film. This variable resistance is shown to be a consequence of slow ion transport through the film. The mechanism of electron transport in such materials is considered and a model of the metal/polymer/electrolyte interface is proposed. © 1980 Elsevier Sequoia S.A.