The catalytic reduction of carbon dioxide to fuels and value-added chemicals is of significance for the development of carbon recycling technologies. One of the main challenges associated with catalytic CO reduction is product selectivity: the formation of carbon monoxide, molecular hydrogen, formate, methanol, and other products occurs with similar thermodynamic driving forces, making it difficult to selectively reduce CO to the target product. Significant scientific effort has been aimed at the development of catalysts that can suppress the undesired hydrogen evolution reaction and direct the reaction toward the selective formation of the desired products, which are easy to handle and store. Inspired by natural photosynthesis, where the CO reduction is achieved using NADPH cofactors in the Calvin cycle, we explore biomimetic metal-free hydride donors as catalysts for the selective reduction of CO to formate. Here, we outline our recent findings on the thermodynamic and kinetic parameters that control the hydride transfer from metal-free hydrides to CO. By experimentally measuring and theoretically calculating the thermodynamic hydricities of a range of metal-free hydride donors, we derive structural and electronic factors that affect their hydride-donating abilities. Two dominant factors that contribute to the stronger hydride donors are identified to be (i) the stabilization of the positive charge formed upon HT via aromatization or by the presence of electron-donating groups and (ii) the destabilization of hydride donors through the anomeric effect or in the presence of significant structural constrains in the hydride molecule. Hydride donors with appropriate thermodynamic hydricities were reacted with CO, and the formation of the formate ion (the first reduction step in CO reduction to methanol) was confirmed experimentally, providing an important proof of principle that organocatalytic CO reduction is feasible. The kinetics of hydride transfer to CO were found to be slow, and the sluggish kinetics were assigned in part to the large self-exchange reorganization energy associated with the organic hydrides in the DMSO solvent. Finally, we outline our approaches to the closure of the catalytic cycle via the electrochemical and photochemical regeneration of the hydride (R-H) from the conjugate hydride acceptors (R). We illustrate how proton-coupled electron transfer can be efficiently utilized not only to lower the electrochemical potential at which the hydride regeneration takes place but also to suppress the unwanted dimerization that neutral radical intermediates tend to undergo. Overall, this account provides a summary of important milestones achieved in organocatalytic CO reduction and provides insights into the future research directions needed for the discovery of inexpensive catalysts for carbon recycling.