A heterojunction photocathode of CuO and CuBi₂O₄ grown on an FTO substrate (FTO/CuO/CuBi₂O₄) was synthesized using hydrothermal method followed by spin coating and annealing to overcome the bottlenecks encountered by CuO in photoelectrochemical (PEC) water splitting application. The synthesis methods, morphological, structural properties, and composition of each sample under each synthesis condition are discussed in detail. The photocathode with 15 coating layers annealed at 450 °C exhibited the best PEC performance. Moreover, its current density reached 1.23 mA/cm² under an applied voltage of − 0.6 V versus Ag/AgCl in a neutral electrolyte. Additionally, it exhibited higher stability than the bare CuO thin film. The bonding of CuBi₂O₄ on CuO resulted in close contact between the two semiconductors, helping the semiconductors support each other to increase the PEC efficiency of the photocathode. CuO acted as the electron-generating layer, and the CuBi₂O₄ layer helped minimize photocorrosion as well as transport the carriers to the electrode/electrolyte interface to accomplish the hydrogen evolution reaction.