Self-passivation in aqueous solution and sluggish surface reaction kinetics significantly limit the photoelectrochemical (PEC)performances of silicon-based photoelectrodes.Herein,a WO3 thin layer is deposited on the p-Si substrate by pulsed laser deposition (PLD),acting as a photocathode for PEC hydrogen generation.Compared to bare p-Si,the single-junctional p-Si/WO3 photoelectrodes exhibit excellent and stable PEC performances with significantly increased cathodic photocurrent density and exceptional anodic shift in onset potential for water reduction.It is revealed that the WO3 layer could reduce the charge transfer resistance across the electrode/electrolyte interface by eliminating the effect of Fermi level pinning on the surface of p-Si.More importantly,by varying the oxygen pressures during PLD,the collaborative modulation of W-O bond covalency and WO6 octahedral structure symmetry contributes to the promoted charge carrier transport and separation.Meanwhile,a large band bending at the p-Si/WO3 junction,induced by the optimized O vacancy contents in WO3,could provide a photovoltage as high as～ 500 mV to efficiently drive charge transfer to overcome the water reduction overpotential.Synergistically,by manipulating W-O local atomic structures in the deposited WO3 layer,a great improvement in PEC performance could be achieved over the single-junctional p-Si/WO3 photocathodes for solar hydrogen generation.