In summary, Park and co-workers have merged Mo:BiVO4 photoelectrocatalysis with enzyme catalysis, using HCO3− as a redox mediator, to achieve stereoselective oxyfunctionalization of C–H bonds. Given the versatility of enzymes in oxidation reactions, biophotoelectrocatalysis holds considerable untapped potential. As in PSII, redox mediators are key to the success of this scheme, as they relieve the oxidative pressure on the enzymes. In short, redox mediators, whether organic or inorganic, link photoinduced electron transfer with the best of redox catalysis across domains, turning solar energy into a driver for challenging and impactful selective organic transformations. Quintessentially, precise spatio-temporal control of local concentration of H2O2 is critical to preventing gradual oxidative deactivation, thereby ensuring the long-term stability of the enzyme under continuous photoelectrochemical operation. Looking ahead, expanding the repertoire of robust redox mediators and engineering more resilient oxygenative biocatalysts could unlock a range of valuable transformations.