Converting and storing solar energy directly as chemical energy through photoelectrochemical devices are promising strategies to replace fossil fuels. Metal oxides are commonly used as photoanode materials, but they still encounter challenges such as limited light absorption, inefficient charge separation, sluggish surface reactions, and insufficient stability. The regulation of surface oxygen species on metal oxide photoanodes has emerged as a critical strategy to modulate molecular and charge dynamics at the reaction interface. However, the precise role of surface oxygen species in metal oxide photoanodes remains ambiguous. The review focuses on elucidating the formation and regulation mechanisms of various surface oxygen species in metal oxides, their advantages and disadvantages in photoelectrochemical reactions, and the characterization methods employed to investigate them. Additionally, the article discusses emerging opportunities and potential hurdles in the regulation of surface oxygen species. By shedding light on the significance of surface oxygen species, this review aims to advance our understanding of their impact on metal oxide photoanodes, paving the way for the design of more efficient and stable photoelectrochemical devices.