Abstract: To help ease the increasingly serious energy crisis and environmental pollution, photoelectrochemical (PEC) water splitting, as a highly promising technology using solar energy, has received widespread research attention. First, Bi2WO6/NiO composite was successfully prepared by a simple spinning annealing method. Compared with the use of pure Bi2WO6, the water oxidation performance of Bi2WO6/NiO photoanode prepared by flame annealing is improved by fourfold. And the best photocurrent reaches 0.04 mA/cm2@1.23 VRHE in 0.5 M Na2SO4, showing an excellent photocatalytic activity and stability. The results show that the formation of Bi2WO6/NiO photoanode can improve the utilization of sunlight, effectively inhibit the carrier recombination, and boost charge transfer performance.