<p>Green plants convert solar energy into energy-rich carbohydrates by utilizing Z-schematic water splitting and CO₂ fixation to realize sustainable photosynthesis. This natural system has inspired biophotoelectrocatalysis, which bridges photo(electro)catalysts and biocatalysts for solar-to-chemical conversion with high specificities under ambient conditions. Here we discuss solar-driven enzymatic systems that can activate a wide range of biocatalysts for versatile synthesis (for example, asymmetric reduction, decarboxylation, cycloaddition, oxygenation and hydroxylation). We explore the mechanisms of photoexcited charge-carrier transfer, emphasizing the role of photoelectrochemical platforms in orchestrating the efficient and selective delivery of photoinduced electrons to redox biocatalysts. This Review highlights recent advances in the field of biophotoelectrocatalysis, including cofactor-dependent or cofactor-free reactions, photoenzymatic chemical transformations, whole-cell photoelectrocatalysis, waste-to-value biorefineries and scalable biosynthesis. Finally, we present future perspectives on the convergence of biotechnology and photoelectrochemical platforms for sustainable solar-driven biosynthesis.</p><p></p>