Investigating the subcellular organization of biomolecules is important for understanding their biological functions. Over the past decade, proximity-dependent labeling methods have emerged as powerful tools for mapping biomolecules in their native context. These methods often capitalize on the in-situ generation of highly reactive intermediates for covalently tagging biomolecules located within nanometers to sub-micrometers of the source of labeling. Among these, photocatalytic proximity labeling methods achieve precise spatial and temporal control of labeling with visible light illumination. In this review, we summarize the mechanisms and applications of existing photocatalytic proximity labeling methods and discuss future opportunities for improving the method.