Tailoring *H Intermediate Coverage on the CuAl₂O₄/CuO Catalyst for Enhanced Electrocatalytic CO₂ Reduction to Ethanol

The direct electrochemical conversion of CO 2 to multi‐carbon products offers a promising pathway for producing value‐added chemicals using renewable electricity. However, producing ethanol remains a challenge because of the competitive ethylene formation and hydrogen evolution reactions. Herein, we propose an active hydrogen (*H)‐intermediate‐mediating strategy for ethanol electroproduction on a layered precursor‐derived CuAl 2 O 4 /CuO catalyst. The catalyst delivered a Faradaic efficiency of 70 % for multi‐carbon products and 41 % for ethanol at current density of 200 mA cm −2 and exhibited a continuous 150 h durability in a flow cell. The intensive spectroscopic studies combined with theoretical calculations revealed that the in situ generated CuAl 2 O 4 could tailor *H intermediate coverage and the elevated *H coverage favors the hydrogenation of the *HCCOH intermediate, accounting for the increased yield of ethanol. This work directs a pathway for enhancing ethanol electroproduction from CO 2 reduction by tailoring *H intermediate coverage.