We report photoelectrochemical hydrogen evolution reaction using a Cu2O-based photocathode with a layer doped with Zn ions. The doping results in the shift of the onset flat-band potential of the photocathode, likely a consequence of maximized band-bending in the Cu2O/Zn : Cu2O heterojunction. Systematic electrochemical analysis reveals that expansion of depletion region is responsible for the enhanced photoelectrochemical performance, e.g., the increase of photocurrent and reduced internal resistance.