This study explores the H2 production performance of CuO/Cu2O with different morphology (nanocubes) synthesized by different methods using different sacrificial reagent (lactic acid), compared with the other three reported CuO/Cu2O photocatalysts used for H2 production. A cubic Cu2O photocatalyst was prepared using a hydrothermal method. It was then calcined at a certain temperature to form a cubic Cu2O/CuO composite photocatalyst. XRD, TEM, and XPS spectra confirmed the successful synthesis of cubic Cu2O/CuO composite photocatalysts by calcination-induced oxidation at a certain temperature. As the calcination temperature increases, the crystal phase of the photocatalyst changes from Cu2O to Cu2O/CuO and then to CuO. The effects of calcination-induced oxidation on morphology, light absorption, the separation of photoexcited carriers, and the H2 production activity of photocatalysts were studied. EPR spectra were monitored to analyze the oxygen vacancies in different samples. Mott–Schottky and Tauc plots were utilized to establish the band structure of the composite photocatalyst. Cu2O/CuO is a type II photocatalyst with a heterogeneous structure that helps to improve electron–hole separation efficiency. The H2 production efficiency of Cu2O/CuO composite photocatalyst reaches 11,888 μmol h−1g−1, 1.6 times that of Cu2O. The formation of the Cu2O/CuO heterojunction leads to enhanced light absorption, charge separation, and hydrogen production activity.