Improved photogenerated carrier separation efficiency is of importance for improving photocatalytic activity. Herein, the photocatalytic CO 2 reduction of a 3D/0D ZnIn 2 S 4 /NiS ohmic‐junction photocatalyst under simulated sunlight is studied. The ZnIn 2 S 4 –2%NiS sample has the best excellent photoreduction CO 2 performance facilitated by triethanolamine (TEOA) reagents, the ZnIn 2 S 4 –2%NiS sample with a CO yield of 12.63 μmol g −1 h −1 , which is two times that for pure ZnIn 2 S 4 (6.37 μmol g −1 h −1 ). It is demonstrated that NiS nanoparticles not only improve the efficiency of electron generation and charge separation by constructing a tight contact ohmic‐junction, but also act as a cocatalyst to extend the photoreaction range and lower the reaction barrier, which effectively accelerates the photocatalytic reduction reaction. Additionally, the 3D structure of ZnIn 2 S 4 has an excellent specific surface area that facilitates the dispersion of NiS. The generation, separation, and migration of photogenerated electron holes are studied from the kinetics perspective through transient photocurrent response, linear sweep voltammetry curve and photoluminescence spectroscopy. In situ Fourier transform infrared spectroscopy is applied to study the CO 2 photoreduction process. Herein, the important role of cocatalyst and ohmic‐junction in improving photocatalytic activity is revealed and a new idea for the construction of efficient photocatalysts is provided.