Platinum phthalocyanine (PtPc) films applied to gold and glassy carbon (GC) surfaces have been shown to exhibit complex electrochemistry in aqueous media. Upon potentiodynamic cycling three anodic (0.81, 1.10 and 1.27 V) and two cathodic peaks (1.12 and 0.59 V vs SCE) develop. These processes are ascribed to phthalocyanine ring oxidation and reduction processes. This phthalocyanine ring electrochemistry is thought to be controlled by anion doping within the film, the large separation between corresponding anodic and cathodic processes being manifestations of barrier potential to anion movement within the film. A large reduction peak at -0.6 V is attributed to the mass expulsion of anions from the film.