Carbon dioxide is a renewable carbon feedstock for the production of chemicals, materials, and fuels.  Photochemical reduction is a promising approach to achieving sustainable CO₂-to-fuel conversion.  Our current research is focused on developing innovative hybrid photocatalysts for use in solar CO₂ reduction.  The photocatalysts are prepared by attaching molecular catalysts onto nanostructured surfaces.  In our study, tricarbonyl Re(I) and macrocyclic Co(III) complexes are chosen as efficient molecular CO₂-reduction catalysts, while mesoporous silicas and TiO₂ nanoparticles are extensively utilized as support for the catalysts.  A variety of techniques, including in situ FTIR spectroscopy, are used to characterize the surface molecular catalysts and follow surface chemistry under photochemical conditions.  Our research highlights the advantages of integrating well-defined molecular catalysts with robust solid-state surfaces in solar energy applications.  Coupling of catalysis with energy sources will be discussed as a key component of artificial photosynthetic assemblies.