Fabrication of bio-electrode systems decorated with redox active biomolecules, flavins, is demonstrated. Exploiting the photochemistry and electrochemistry of flavins, we explored the photo-electrochemical activity of flavin-functionalized electrode systems to assess their potential utility for sustainable energy production. As model systems, lumiflavin and flavin adenine dinucleotide were immobilized on carbon electrodes by dropcasting and covalent grafting techniques. Activity of these bio-electrodes towards generation of O2 from H2O in 0.5 M potassium phosphate buffer at pH 7.1 was demonstrated. Irradiation of the electrode system with visible light led to increased activity of the electrodes with a 3-fold enhancement of oxidation of H2O.