Solar energy is undoubtedly the largest and most economical source of clean energy. However, it currently supplies no more than 2% of the world's energy demand. [1] Moreover, solar energy is diffuse and must be converted by high-performance photocatalyst with the following characteristics: 1) high stability to various electrolytes (corrosive environments), 2) degradation resistance during long-time sunlight exposure, 3) band energetics suitable for the efficient and continuous production of fuels, and (most importantly) 4) fast primary processes that drive the charge-carrier generation, recombination, trapping, and transfer. The processes listed in (4) are essential for optimizing the final performance of a photoelectrode. [2][3][4] In recent years, researchers have explored various nanostructured materials to meet the abovementioned requirements. [5][6][7][8][9] Despite considerable progress in material design and synthesis, the performance in specific processes should be further improved. Photoelectrochemical (PEC) CO 2 reduction is an attractive approach for converting CO 2 into value-added chemical feedstocks (such as CO, CH 4 , CH 3 OH, and HCOOH). [10] However, as clarified in recent findings, junction architectures combining compounds with multifunctional properties can only meet the uphill energy demands of CO 2 reduction. [11] Hybrid CuO/Cu 2 O can be combined with other semiconductors or/and charge transporting layers, forming heterojunctions that improve the photocatalytic performance of an overall system. One drawback of this junction architecture is poor adhesion between the compounds, which causes loss of the catalytic active sites through aggregation or desorption into the