It has been found that poly(o-phenylenediamine)(PoPD) electrochemically prepared shows considerable solubility in organic media and PoPD is most soluble in dimethyl sulfoxide (17.0 g dm(-3)). The spectroscopic, scanning tunneling microscopic and electrochemical characterization of the virgin and recast (reprocessed) films of PoPD has been studied, and the results compared. In both films, the anodic peak at -0.05 V vs. see was responsible for the color change of the film from transparent yellow to red brown. However, the electrochemical reversibility of the recast film was much worse than that of the virgin film. This was attributed to the crowded stacking of the former polymer chains which prevented counter anions from being readily undoped.