<p>Electrochemically mediated CO₂ capture offers a promising alternative to thermochemical capture, but benchmark sorbents possess an undesired trade-off: strong CO₂ binding necessitates a highly negative reduction potential, driving undesirable oxygen reduction. Meanwhile, more positive potentials compromise binding. Here we circumvent this trade-off using N-heterocyclic imines (NHIs), which exhibit a tailorable CO₂ binding strength (~50–100 kJ mol⁻¹ CO₂) in the neutral state and release CO₂ upon electro-oxidation, distinct from prevailing molecular capture mechanisms. Whereas initial NHI structures exhibited redox irreversibility due to solvent-based hydrogen abstraction, a phenylene-linked bis(NHI) design achieves redox reversibility by charge delocalization on the benzene ring, which simultaneously enables a 2 CO₂ per e⁻ swing. A symmetric electrochemically mediated CO₂ capture system demonstrated stable cycling performance over 40 cycles and operated &gt; 500 mV more positive than the oxygen reduction reaction, with projected theoretical minimum energy consumption of ~10 kJ mol⁻¹ CO₂ and a system work of 28–43 kJ mol⁻¹ CO₂ under 5–15% CO₂.</p>