The cost‐effective, robust, and efficient electrocatalysts for photoelectrochemical (PEC) water‐splitting has been extensively studied over the past decade to address a solution for the energy crisis. The interesting physicochemical properties of CuO have introduced this promising photocathodic material among the few photocatalysts with a narrow bandgap. This photocatalyst has a high activity for the PEC hydrogen evolution reaction (HER) under simulated sunlight irradiation. Here, the recent advancements of CuO‐based photoelectrodes, including undoped CuO, doped CuO, and CuO composites, in the PEC water‐splitting field, are comprehensively studied. Moreover, the synthesis methods, characterization, and fundamental factors of each classification are discussed in detail. Apart from the exclusive characteristics of CuO‐based photoelectrodes, the PEC properties of CuO/2D materials, as groups of the growing nanocomposites in photocurrent‐generating devices, are discussed in separate sections. Regarding the particular attention paid to the CuO heterostructure photocathodes, the PEC water splitting application is reviewed and the properties of each group such as electronic structures, defects, bandgap, and hierarchical structures are critically assessed.

Cu₂O and CuO thin films deposited by a sol–gel spin-coating process show promise for photocatalytic water splitting.