Owing to their remarkable success in photocatalytic applications, multiferroic BiFeO₃ and its derivatives have gained a highly promising position as electrode materials for future developments of efficient catalysts. In addition to their appropriate band gaps, these materials exhibit inherent intrinsic polarizations enabling efficient charge carrier separation and their high mobility without the need for additional co-catalysts. Here, we review the existing strategies for enhancing the photocatalytic performances of BiFeO₃-based materials and we describe the physico-chemical properties at the origin of their exceptional photocatalytic behavior. A special focus is paid to the degradation of organic pollutants and water splitting, both driven through photocatalysis to unveil the correlation between BiFeO₃ size, substitution, and doping on the one hand and the photocatalytic performances on the other hand. Finally, we provide practical recommendations for future developments of high-performing BiFeO₃-based electrodes.