Synthetic organic pigments from the direct discharge of textile effluents are considered as colossal global concern and attract the attention of scholars. The efficient construction of heterojunction systems involving precious metal co-catalysis is an effective strategy for obtaining highly efficient photocatalytic materials. Herein, we report the construction of a Pt-doped BiFeO3/O-g-C3N4(Pt@BFO/O-CN) S-scheme heterojunction system for photocatalytic degradation of aqueous rhodamine B (RhB) under visible-light irradiation. The photocatalytic performances of Pt@BFO/O-CN and BFO/O-CN composites and pristine BiFeO3and O-g-C3N4were compared, and the photocatalytic process of the Pt@BFO/O-CN system was optimized. The results exhibit that the S-scheme Pt@BFO/O-CN heterojunction has superior photocatalytic performance compared to its fellow catalysts, which is due to the asymmetric nature of the as-constructed heterojunction. The as-constructed Pt@BFO/O-CN heterojunction reveals high performance in photocatalytic degradation of RhB with a degradation efficiency of 100% achieved after 50 min of visible-light irradiation. The photodegradation fitted well with pseudo-first-order kinetics proceeding with a rate constant of 4.63 × 10−2min−1. The radical trapping test reveals that h+and•O2−take the leading role in the reaction, while the stability test reveals a 98% efficiency after the fourth cycle. As established from various interpretations, the considerably enhanced photocatalytic performance of the heterojunction system can be attributed to the promoted charge carrier separation and transfer of photoexcited carriers, as well as the strong photo-redox ability established. Hence, the S-scheme Pt@BFO/O-CN heterojunction is a good candidate in the treatment of industrial wastewater for the mineralization of organic micropollutants, which pose a grievous threat to the environment.