The invention relates to a preparation method of a Ni single atom/oxygen defect copper tungstate photo-anode, and belongs to the technical field of photoelectrocatalysis. According to the project, a one-dimensional CuWO4 hollow nanofiber photo-anode with a high specific surface area is used as a carrier, a surface defect engineering strategy is adopted, and a Co monatomic electrocatalyst is anchored through oxygen vacancies on the surface of CuWO4. The single atom loading process can avoid a high-temperature calcination step, a new method is provided for uniform dispersion of Ni single atoms on the surface of the copper tungstate photoelectrode, and the prepared Ni single atom/oxygen defect copper tungstate photoanode can realize high-activity and high-stability water decomposition and hasa wide application prospect in the field of hydrogen energy preparation.