A novel Cu2O-Au-BFO heterostructure photocathode was constructed which significantly improved the efficiency of photo-generated carrier transfer for solar hydrogen production. A BiFeO3 (BFO) ferroelectric film was synthesized on top of a Cu2O layer by a sputtering process. The BFO layer acted to protect the Cu2O layer from photochemical corrosion, increasing photoelectrochemical (PEC) stability. The p-n heterojunction between Cu2O and BFO layers enhanced the PEC properties by suppressing charge recombination and improved interfacial charge transfer efficiency. When Cu2O and BFO are interfaced by Au Nanoparticles (NPs) the PEC performance was further enhanced, due to hot-electron transfer at the plasmonic resonance. After positive poling, the depolarization field across the whole volume of BFO film drove electrons into the electrolyte solution, inducing a significant anodic shift, Vop of 1.01 V vs. RHE, together with a significantly enhanced photocurrent density of -91 μA/cm2 at 0 V vs. RHE under 100 mW/cm2 illumination. The mechanism was investigated through experimental and theoretivcal calculations.