A multicomponent hybrid photocathode based on PCN that is capable of selective reduction of O2 to H2O2 under visible light irradiation (420 nm LED) is reported for the first time. The optimized photocathode architecture comprises PCN deposited on a porous NiOx film acting as a scaffold for effective extraction and collection of photogenerated holes, whereby a TiO2 interlayer between NiOx and PCN is found to exert a beneficial effect on the overall photoelectrocatalytic performance. The latter effect can be understood by assuming the formation of a p/n junction between the NiOx and TiO2 layers, as known from the literature . However, our photocurrent and XPS measurements also suggest that this is associated with the generation of intra-gap states that provide an explanation for the significant visible light photocurrent response of NiOx-TiO2 photoelectrodes and render the TiO2 layer effectively "leaky" with respect to the transport of holes. Importantly, most of the studies on photocatalytic H2O2 production using PCN-based photocatalysts reported so far have been carried out in the presence of additional (sacrificial) electron donors such as aliphatic or aromatic alcohols. The fact that our PCN-based photocathodes catalyze the light-driven reduction of O2 to H2O2 in the absence of any additional electron donor confirms unambiguously that PCN materials are inherently photocatalytically active in H2O2 production. This significant finding thus paves the way for the development of further PCN-based photocathodes in which PCN could be coupled to more effective light absorbers in order to increase the overall performance. These efforts could eventually culminate in the construction of complete tandem devices comprising wellmatched photocathodes and photoanodes, which would allow for bias-free operation in the light-driven selective synthesis of high-value commodity chemicals .