Photoelectrochemical (PEC) devices that use semiconductors to absorb solar light for water splitting offer a promising way toward the future scalable production of renewable hydrogen fuels. However, the charge recombination in the photoanode/electrolyte (solid/liquid) junction is a major energy loss and hampers the PEC performance from being efficient. Here, we show that this problem is addressed by the conformal deposition of an ultrathin p-type NiO layer on the photoanode to create a buried p/n junction as well as to reduce the charge recombination at the surface trapping states for the enlarged surface band bending. Further, the in situ formed hydroxyl-rich and hydroxyl-ion-permeable NiOOH enables the dual catalysts of CoO(x) and NiOOH for the improved water oxidation activity. Compared to the CoO(x) loaded BiVO4 (CoO(x)/BiVO4) photoanode, the ∼6 nm NiO deposited NiO/CoO(x)/BiVO4 photoanode triples the photocurrent density at 0.6 V(RHE) under AM 1.5G illumination and enables a 1.5% half-cell solar-to-hydrogen efficiency. Stoichiometric oxygen and hydrogen are generated with Faraday efficiency of unity over 12 h. This strategy could be applied to other narrow band gap semiconducting photoanodes toward the low-cost solar fuel generation devices.