<p>Despite their weak nature, non-covalent interactions are fundamental to chemical systems, shaping a wide spectrum of physicochemical processes. Defined by their tunable strength, reversibility, and environmental sensitivity, they are central to molecular recognition, the assembly and stabilization of molecular architectures, and the modulation of reaction pathways at both the molecular and supramolecular levels. In recent years, the intentional incorporation of non-covalent donor or acceptor sites into homogeneous and heterogeneous catalysts has emerged as a powerful strategy to enhance control over catalytic selectivity and efficiency. By mimicking nature’s reliance on weak yet cooperative interactions, chemists have unlocked new routes for designing catalysts that can fine-tune reaction environments. In this Review, we provide an overview of recent advances that underscore the auxiliary and often crucial role of non-covalent interactions in the electrochemical reduction reaction of CO₂ (CO₂RR). Following a brief discussion of their fundamental nature and influence on electrocatalytic processes, we examine representative cases in which non-covalent interactions emerge as pivotal, sometimes in unexpected ways, in shaping reactivity and selectivity.</p> Graphical abstract <p></p>