The construction of S-scheme heterojunctions via exploring semiconductors with suitable energy band structures can effectively improve the photocatalytic performance of TiO2. In this work, CuCoSe2/TiO2 heterojunction were prepared using solvent evaporation strategy by their different surface charge properties. The investigation indicates that rates of H2 evolution (rH2) of the system increases significantly from 138.1 (TiO2) to 3773.8 μmol·g−1·h−1 (CuCoSe2/TiO2). It is found that the incorporation of CuCoSe2 can extend the visible light absorption range of the system, increase the electrochemically active surface area, facilitate charge generation and decrease the transfer resistance, reduce the H2 production overpotential and the water contact angle. Further investigation reveals that a bimetallic selenide CuCoSe2 exhibit superior enhancement activity compared to their monometallic selenides (CuSe2, CoSe2) due to the synergistic effect of Co and Cu. Especially, the charge transfer between CuCoSe2 and TiO2 follows S-scheme charge separation route, which can effectively enhance charge separation/migration, reserve e− with strong reducing ability in TiO2, thereby promoting the H2 evolution kinetics. Moreover, the heterojunction also demonstrates exceptional stability throughout the cycle experiment. The present work establishes an experimental basis for the advancement of highly efficient and stable bimetallic selenides related heterojunctions in the field of photocatalytic H2 evolution.