Spin Polarized Chiral Co 3 O 4 Boosts High‐Pressure CO 2 Electroreduction to Ethanol With 90% Selectivity

ABSTRACT Electrocatalytic CO 2 reduction (CO 2 RR) to value‐added multicarbon products using non‐copper‐based catalysts remains a major challenge, especially for selective ethanol production. Herein, we report that chiral Co 3 O 4 featuring strong electron spin polarization achieves a maximum ethanol Faradaic efficiency of 90% at ‐0.9 V versus NHE in KHCO 3 electrolytes under a 30 bar CO 2 pressure, substantially outperforming both racemic Co 3 O 4 and previously reported non‐copper‐based catalysts. The enhanced spin polarization in chiral Co 3 O 4 facilitates electron transfer and promotes the activation of the adsorbed CO 2 , while also lowering the free energy change for C–C coupling to form *COCHO intermediate, thereby promoting ethanol production. Our work establishes spin polarization as a key determinant for efficient C–C coupling on non‐copper‐based catalysts and provides mechanistic principles for the rational design of CO 2 RR electrocatalyst.