ReSsub.2-based heterostructures, which involve the coupling of a narrow band-gap semiconductor ReSsub.2 with other wide band-gap semiconductors, have shown promising performance in energy conversion and environmental pollution protection in recent years. This review focuses on the preparation methods, encompassing hydrothermal, chemical vapor deposition, and exfoliation techniques, as well as achievements in correlated applications of ReSsub.2-based heterostructures, including type-I, type-II heterostructures, and Z-scheme heterostructures for hydrogen evolution, reduction of COsub.2, and degradation of pollutants. We believe that this review provides an overview of the most recent advances to guide further research and development of ReSsub.2-based heterostructures for photocatalysis.