Photosynthesis powers living cells through the photogeneration of electron-hole pairs that drive energy-demanding chemical reactions. The principles that enable photosynthesis and biological energy conversion also provide a foundation for advancing the development of artificial, light-driven systems for catalytic production of chemical fuels. In order to effectively couple catalysts with light-harvesting requires understanding how molecular interfaces support electron transfer processes and the dynamics of the catalytic reaction. To advance understanding on this topic we have been investigating molecular complexes that integrate reduction-oxidation enzymes with light-harvesting materials to probe mechanisms coupling catalysis to photoexcited electron transfer. A combination of transient, and steady-state infrared and paramagnetic spectroscopy techniques are being used to gain insight on how photoexcited electrons couple to enzymes to drive multi-step reduction reactions. A summary of our research progress on these topics will be presented.