To help China achieve its goal of carbon neutrality, a CuO/BiOCl heterostructure with enhanced electron-induced interfacial interactions and improved CO₂ photoreduction performance was hydrothermally synthesized in situ. The electrons originating from the surface residual CTAB & urea reacted with the CuO component to generate Cu₂O, and between them BiOCl played the bridged role to transfer the electrons, which strengthened the intense contact between the two components, thus harvesting light and promoting the segregation and transfer efficiency of the photogenerated carriers. Furthermore, the greater number of generated electrons could enhance the activation of CO₂, which could decrease the energy barriers of the thermodynamically stable CO₂ and especially promote the formation of CO₂-reduced intermediates (HCOOH, HCO₃^–). As a result, the CO₂ photoreduction performance of the electron-induced heterostructure of CuO/BiOCl composites exhibited higher CH₄ and CH₃OH yields than neat CuO or BiOCl, in which the optimized BC2 photocatalyst (2% mass ratio of CuO to BiOCl) reached 114.1 μmol·h⁻¹·g⁻¹ CH₄ and 36.2 μmol·h⁻¹·g⁻¹ CH₃OH. This work provided a new strategy to synthesize efficient heterojunctions that can improve the photocatalytic reduction of CO₂; these heterojunctions were constructed with a strong interaction interface via self-electron-reduction.