The conversion of carbon dioxide to fuels is a promising approach to sustainable energy storage. Selective and efficient reduction of CO2 to fuels (or fuel precursors) relies on advanced catalysts. Guided by the detailed mechanistic insights available from studies of molecular catalysts, we are developing broad strategies and structural design principles for CO2 reduction reactions. Selective CO generation is accomplished with ruthenium and iron complexes that pair a redox-active supporting ligand with a strongly donating ligand featuring an N-heterocyclic carbene (NHC). A key role of the trans effect in electrocatalytic CO2 reduction is revealed through these catalysts. Looking beyond CO to fuels that are energy-dense liquids or contain carbon–carbon bonds, cascade catalysis strategies combining electrochemical and thermal organometallic catalysts will be presented.