S-scheme heterojunction photocatalysts featuring efficient charge transport paths provide a promising strategy for cooperative achieving photocatalytic CO2 reduction reaction (CO2RR) and Rhodamine B (RhB) degradation. In this work, S-scheme heterojunctions composed of g-C3N4 nanosheets coated on Bi2WO6 nanosheets were prepared by a one-step hydrothermal method, resulting in broad-spectrum light absorption, high electron–hole separation efficiency, and excellent photocatalytic CO2 reduction and RhB oxidization performance. Mechanistic analysis revealed the formation of a directional charge transport path at the interface of the heterojunction, which maintained a high oxidation and reduction potential and improved the efficiency of photoexcited carrier separation. In particular, the synergistic reaction system showed excellent photoredox activity compared with the two separate half-reactions. The optimal catalyst 15CN/BWO displayed the highest CO2 conversion efficiency, with CO and CH4 generation rates of 4.3 and 2.7 μmol g−1h−1, respectively, and the degradation efficiency of the composite heterojunction was significantly higher than that of its constituent materials. This work provides a new possibility for designing a novel dual-function photocatalytic reaction system.