The social demand for energy is highly increasing because of the rapid development of economy. On the other hand, environmentally safe treatment of industrial wastewater is required to raise to a higher standard. Photocatalytic fuel cell (PFC), which adopts the photocatalytic electrode in the fuel cell configuration, can achieve the dual functions of efficient degradation of organic pollutant and simultaneous electricity generation. Therefore, PFC promises to have potential applications in harmless disposal and resource utilization of wastewater. The photocatalytic electrode is the core component of PFC system. The enhancement for the light activation of the photocatalytic electrode and the improvement of the separation rate of photogenerated carriers become the key strategies to improve the performance. In addition, the reactor design and optimization of operational parameters are also beneficial to improve the PFC performance. In this review, the basic principle of PFC has been introduced, and the progress of PFC in the treatment of environmental pollutants has also been reviewed. The optimization of PFC system for enhancing the pollution control performance and electricity generation efficiency has also been discussed in detail. This review provides theoretical guidance for further research of efficient and stable PFC systems for the wastewater treatment and energy recovery.