Precise arrangement of multivalent Cu sites for the synchronized activation of CO ₂ and H ₂ in selective methanol synthesis remained challenging. Herein, we designed spatially arrayed Cu ⁺ ‐Cu ⁰ cluster pairs confined within UiO‐66 (U66) to achieve spatiotemporally directed CO ₂ hydrogenation to methanol. This architecture was constructed by creating missing‐linker defects within U66 using L‐ascorbic acid (LA), followed by sequential anchoring of high‐density, adjacent Cu ⁺ ‐Cu ⁰ cluster pairs (≈1:1 ratio) to yield a Cu/U66(LA‐Cu) catalyst. Under reaction conditions of 220°C and 3 MPa, this catalyst achieved a methanol space‐time yield of 688.1 mg·g ⁻¹ ·h ⁻¹ and an ultra‐high methanol selectivity (97.0%). Its unity‐methanol selectivity was 1.06–1.77 times that of high‐stability oxide materials. Meanwhile, catalyst's stability of 200 h was significantly prolonged compared to high‐selectivity MOF‐based catalysts that operated stably for 60–175 h. Mechanistic studies revealed that Cu ⁺ ‐Cu ⁰ cluster pairs within defective U66 not only enabled partitioned synergistic activation of CO ₂ and H ₂ , but established an efficient electron/hydrogen transfer pathway. This facilitated the migration of active hydrogen species to CO ₂ adsorption sites, where adsorbed CO ₂ was converted into CO intermediates and underwent deep hydrogenation. This structural design synergistically enhanced compatibility between H ₂ dissociation and CO ₂ hydrogenation steps, enabling reaction to proceed efficiently along the RWGS + CO‐hydro pathway.

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