Reduction of CO2 by electrochemical and photoelectrochemical methods to produce carbon-rich fuels is a heavily pursued research theme. Most of the current efforts are focused on the development of transition-metal-based catalysts. In this tutorial review, we present an overview of the development of organic molecules as mediators and catalysts for CO2 reduction. Four classes of organic molecules are discussed: tetraalkylammonium salts, aromatic esters and nitriles, ionic liquids, and pyridinium derivatives. It is shown that reactions mediated or catalyzed by these organic molecules can be competitive compared to their metal-catalyzed counterparts, both in terms of product selectivity and energy efficiency.