This study describes how the optimization of Cu2O/CuO heterostructures can enhance their (photo)catalytic performance. More specifically, the evaluation of catalysts with different Cu2O/CuO molar ratios was used to optimize their performance for the hydrogenation of 4-nitrophenol under both blue-LED light and dark conditions. For the first time, we analyzed the effect of blue LED irradiation on this reaction and found that when blue LEDs are used as the light source, a Cu2O/CuO ratio of 0.15 results in rate constants 7 to 3 times higher than those of catalysts with either lower (0.01) or higher (0.42) ratios. Furthermore, this photocatalyst shows good stability, >70% after 5 cycles, and excellent chemoselectivity in the selective reduction of the nitro group in the presence of other functionalities, i.e. -COOH, -CONH2 and -OH.