Biochar has attracted significant attention due to its excellent environmental benefits and extensive applications. Recently, a consensus has been accepted that biochar can act as a photocatalyst and trigger effective photocatalytic reactions in the environment, which is important to energy conversion and the cycle of elements. However, its photocatalytic processes and the corresponding environmental impacts need to receive more and due attention. In this review, we provide a comprehensive summary of the underlying correlations among the pyrolytic evolution of biomass, the structure characteristic of biochar, and the resultant photocatalytic performance. Moreover, the photocatalytic processes and the influence of environmental factors were elaborately investigated on biochar. Finally, future tendencies and challenges in the photocatalysis of biochar have been prospected in the environmental field. This review has offered innovative insights into the photocatalytic essential of biochar and highly enhanced the understanding of its environmental impact.