AbstractStabilizing atomically dispersed single atoms (SAs) on silicon photoanodes for photoelectrochemical-oxygen evolution reaction is still challenging due to the scarcity of anchoring sites. Here, we elaborately demonstrate the decoration of iridium SAs on silicon photoanodes and assess the role of SAs on the separation and transfer of photogenerated charge carriers. NiO/Ni thin film, an active and highly stable catalyst, is capable of embedding the iridium SAs in its lattices by locally modifying the electronic structure. The isolated iridium SAs enable the effective photogenerated charge transport by suppressing the charge recombination and lower the thermodynamic energy barrier in the potential-determining step. The Ir SAs/NiO/Ni/ZrO₂/n-Si photoanode exhibits a benchmarking photoelectrochemical performance with a high photocurrent density of 27.7 mA cm⁻² at 1.23 V vs. reversible hydrogen electrode and 130 h stability. This study proposes the rational design of SAs on silicon photoelectrodes and reveals the potential of the iridium SAs to boost photogenerated charge carrier kinetics.