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In this study, a bipolar visible light responsive photocatalytic fuel cell (PFC) was constructed by loading a Z-scheme g-C3N4/carbon black/BiOBr and a Ti3C2/MoS2Schottky heterojunction on the carbon brush to prepare the photoanode and photocathode, respectively. It greatly improved the electron transfer and achieved efficient degradation of organic pollutants such as antibiotics and dyes simultaneously in two chambers of the PFC system. The Z-scheme g-C3N4/carbon black/BiOBr formed by adding highly conductive carbon black to g-C3N4/BiOBr not only effectively separates the photogenerated carriers, but also simultaneously retains the high reduction of the conduction band of g-C3N4and the high oxidation of the valence band of BiOBr, improving the photocatalytic performance. The exceptional performance of Ti3C2/MoS2Schottky heterojunction originated from the superior electrical conductivity of Ti3C2MXene, which facilitated the separation of photogenerated electron–hole pairs. Meanwhile, the synergistic effect of the two photoelectrodes further improved the photocatalytic performance of the PFC system, with degradation rates of 90.9% and 99.9% for 50 mg L−1tetracycline hydrochloride (TCH) and 50 mg L−1rhodamine-B (RhB), respectively, within 180 min. In addition, it was found that the PFC also exhibited excellent pollutant degradation rates under dark conditions (79.7%, TCH and 97.9%, RhB). This novel pollutant degradation system is expected to provide a new idea for efficient degradation of multiple pollutant simultaneously even in the dark.