Efficient copper based thin film solar cells usually use inorganic n-type semiconductor material CdS as the buffer layer. Therefore, the interface quality and energy band matching between the buffer layer and the absorption layer are crucial to the collection and utilization of carriers. Heat treatment can promote the mutual diffusion of interface elements, the migration of ions in the material, and the change of defect state, and the appropriate temperature will change the Cu-Zn ordering degree in the absorption layer, so as to improve the efficiency of the solar cells. Based on the optimization of CdS basic process, the strategy of annealing CdS/copper-based thin film heterojunction in sulfur atmosphere further improves the quality of CdS thin film, and is applied to copper-based solar cells to regulate the p-n heterojunction energy band gap matching of copper-based thin film cells. The results show that the annealing of CdS thin film in sulfur-containing inert atmosphere can effectively improve the crystal quality of CdS thin film and inhibit the non-radiative recombination loss caused by defect trapping at the interface of CZTS/CdS heterojunction, and the open-circuit voltage of the device can significantly increase to 718 mV. In addition, annealing CZTS/CdS heterojunction in S/Ar atmosphere can effectively improve the p-n heterojunction energy band gap matching, which not only improves the electron transmission, but also reduces the carrier recombination, thus improving the V _ocand FF of the device. Besides, the oxygen element in CdS film can be replaced by sulfur element in sulfur atmosphere to improve the quality of CdS film, and thus enhancing the short-wave absorption of solar cell device. Therefore, in terms of device efficiency, the efficiency of CZTS solar cell based on sputtering method increases from 3.47% to 5.68%, which is about twice that of non-annealing treatment. Its device structure is Glass/Mo/CZTS/CdS/i-ZnO/Al:ZnO/Ni/Al, providing a reliable process window for copper based thin film solar cell devices to achieve high open-circuit voltage. Meanwhile, this study strongly demonstrates the importance of annealing atmosphere selection for CdS quality and energy band matching of CZTS/CdS heterojunction. In addition to interface interdiffusion, the composition and crystallinity of thin film material are controlled.