Photoelectrochemical (PEC) cells provide a promising solution for the synthesis of hydrogen peroxide (H2O2). Herein, an integrated photocathode of p-type BiVO4 (p-BVO) array with tetragonal zircon structure coupled with different metal oxide (MOx, M = Sn, Ti, Ni, and Zn) heterostructure and NiNC cocatalyst (p-BVO/MOx/NiNC) was synthesized for the PEC oxygen reduction reaction (ORR) in production of H2O2. The p-BVO/SnO2/NiNC array achieves the production rate 65.46 μmol L–1 h–1 of H2O2 with a Faraday efficiency (FE) of 76.12%. Combined with the H2O2 generation of water oxidation from the n-type Mo-doped BiVO4 (n-Mo:BVO) photoanode, the unbiased photoelectrochemical cell composed of a p-BVO/SnO2/NiNC photocathode and n-Mo:BVO photoanode achieves a total FE of 97.67% for H2O2 generation. The large area BiVO4-based tandem cell of 3 × 3 cm2 can reach a total H2O2 production yield of 338.84 μmol L–1. This work paves the way for the rational design and fabrication of artificial photosynthetic cells for the production of liquid solar fuel.