In connection with studies on the photographic properties of the photocatalytic deposition of palladium and the electrochemical properties of were investigated. In order to study both phenomena simultaneously the experiments were performed with thin, layers deposited on a conducting substrate. It could be shown that the primary step is an anodic photocurrent (O2 evolution) which catalyzes the cathodic deposition of palladium under open‐circuit conditions. Various parameters such as space charge effects, film thickness, and doping were studied and are discussed in detail.