Redox biocatalysis has come to the forefront because of its excellent catalytic efficiency, stereoselectivity, and environmental benignity. The green and sustainable biotransformation can be driven by photoelectrochemical (PEC) platforms where redox biocatalysis is coupled with photoelectrocatalysis. The main challenge is how to transfer photoexcited electrons to (or from) the enzyme redox centers for effective biotransformation using solar energy. This review commences with a conceptual discussion of biocatalytic PEC platforms and highlights recent advances in PEC-based biotransformation through cofactor regeneration or direct transfer of charge carriers to (or from) oxidoreductases on enzyme-conjugated electrodes. Finally, we address future perspectives and potential next steps in the vibrant field of biocatalytic photosynthesis.