Electrophile–Nucleophile Paired Heteronuclear Dual‐Site for Selective CO 2 Photoreduction to Ethanol via Oxygen‐Tethered Asymmetric C–C Coupling

ABSTRACT Photocatalytic CO 2 reduction to valuable multicarbon products like ethanol is a promising strategy for solar energy conversion, yet remains challenged by kinetically constrained C–C coupling and competitive C–O cleavage toward ethylene. Herein, an electrophile‐nucleophile pairing strategy is developed by constructing atomically Cu–Zr heteronuclear dual sites within a porphyrinic framework, which can simultaneously reduce repulsion for C–C coupling and strengthen the C–O bond. The electron‐deficient Zr, as a strong oxygen‐affixed anchor, stabilizes critical *OCH intermediates via O‐coordination, while adjacent electron‐rich Cu sites drive *CO adsorption—inducing charge asymmetry between *OCH and *CO for kinetically favored dimerization. Subsequent hydrogenation selectively proceeds toward ethanol due to enhanced Zr–O stabilization that prevents C–O scission. The optimized catalyst achieved a near‐unity ethanol selectivity at 87.8 µmol·g −1 ·h −1 using water as a scavenger under a CO 2 pressure of 0.5 MPa, which further increased to 195.1 µmol·g −1 ·h −1 at 1.5 MPa. This work establishes mismatched electrophile‐nucleophile pairs as a versatile design principle for steering photocatalytic CO 2 reduction toward value‐added multicarbon products.