<p>Pyridoxal and its derivatives play crucial roles in mediating a diverse range of reactions in both enzyme-catalysed and chemically synthesized transformations. Here, inspired by nature, we have established a dual Co/pyridoxal electrocatalysis that tames radical intermediates for asymmetric transformations, thereby surpassing natural capabilities and uncovering catalytic processes to produce high-value quaternary amino esters with excellent enantioselectivity and functional-group tolerance. Distinctive chiral cobalt catalysts with ligands derived from cinchona alkaloid have been designed to mimic enzyme function, regulating the chiral cavity and creating an optimal chiral environment that consistently coordinates aldimine and electrochemically induced azaallyl radical intermediates to induce excellent stereoselectivity in biomimetic polar and radical reactions. Such enzyme-inspired electrocatalysis introduces a strategy for stereoselective intermolecular radical reactions, unlocking a potent platform for sustainable enantioselective synthesis.</p><p></p>