Constructing Schottky junctions is a potent strategy for enhancing charge separation and charge dynamics, essential for optimizing the kinetics of efficient CO2 photoreduction reactions (CO2 RR). Yet, developing highly efficient Schottky heterojunction photocatalyst continues to be a formidable challenge. Here, we utilize two-step hydrothermal technology to prepare a BiOCl/NiS Schottky heterojunction with a powerful internal electric field (IEF) to accelerate the photo-conversion of CO2 to CO. Experimental results show that the charge separation efficiency and IEF strength of the BiOCl/NiS composite photocatalyst are 1.26 and 5.63 times those of BiOCl, respectively. In addition, the BiOCl/NiS composite sample has excellent light absorption ability. Under Uv–vis light irradiation, the BiOCl/NiS sample exhibits superior CO2 to CO photoreduction activity without any sacrificial agents, and a CO yield reaching 7.97 μmol⋅g−1⋅h−1, which is 2.97 times higher than that of BiOCl (2.68 μmol⋅g−1⋅h−1). This work provides a viable solution for designing efficient and stable Schottky junction composite materials.