The nature and relative amounts of the different species present in the surface region of and film electrodes, before and after an anodic polarization in solution, have been determined by means of x‐ray photoelectron spectroscopy. The existence of a surface defect structure of , analogous to that found on powder, has been confirmed for both the and electrodes. Two different chlorine species, identified as chloride ions and adsorbed atomic chlorine, have been shown to be present on the surface of the electrodes used as anodes for the chlorine evolution.