Biocatalytic photosynthesis combines the distinctive characteristics of redox biocatalysis and photocatalysis for solar-to-chemical conversion. Photocatalytic materials harvest renewable solar light to activate oxidoreductases that offer nature-inspired routes for sustainable chemical synthesis with unparalleled reaction selectivity. Here we begin with a conceptual discussion on solarpowered redox biocatalysis, describe the underlying molecular mechanisms and thermodynamics, and highlight recent advances in: (i) photocatalytic activation of cell-free or whole-cell biocatalytic machineries (e.g., redox enzymes, acetogens, cyanobacteria); (ii) repurposing cofactor-dependent enzymes for their new-to-nature syntheses; (iii) chemical transformations by photoenzymes; and (iv) photoelectrocatalytic biosynthesis.