Herein, we report for the first time a multicomponent hybrid photocathode based on PCN for selective reduction of O2 to H2O2 under visible light irradiation (420 nm LED), whereby the desired H2O2 product is determined in-situ using microelectrodes. The optimized photocathode architecture comprises PCN deposited on a porous NiOx film acting as a scaffold for effective extraction and collection of photogenerated holes. A detailed analysis of various photoelectrode configurations shows that the presence of PCN is crucial for obtaining H2O2 as a product, and provides evidence for the beneficial effect of a TiO2 interlayer on the overall photoelectrocatalytic performance.