To develop a new and efficient CO2‐to‐methanol catalyst is of extreme significance but still remains a challenge. Herein, an innovative indirect two‐step strategy is reported to synthesize a highly efficient capsule‐structured copper‐based CO2‐to‐methanol catalyst (CZA‐r@CZM). It consists of a structurally reconstructed millimeter‐sized Cu/ZnO/Al2O3 core (CZA‐r) with intensified Cu–ZnO interactions, which is made by a facile hydrothermal treatment in an alkaline aqueous solution, and a Cu/ZnO/MgO (CZM) shell prepared by an ethylene glycol‐assisted physical coating method. The CZA‐r core displays 2.7 times higher CO2 hydrogenation activity with 2.0 times higher CO selectivity than the previously reported Cu/ZnO/Al2O3 (CZA‐p), whereas the CZM shell can efficiently catalyze hydrogenation of the as‐formed CO from the CZA‐r core to methanol as it passes through the shell. As a result, the developed capsule‐structured CZA‐r@CZM catalyst exhibits 2.4 times higher CO2 conversion with 1.8 times higher turnover frequency and 2.3‐fold higher methanol space–time yield than the CZA‐p catalyst (729.8 vs. 312.6 gMeOH kgcat−1 h−1). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) experiments reveal that the CO2 hydrogenation reaction proceeds through a reverse water–gas shift reaction followed by a CO hydrogenation pathway via an *H3CO intermediate. This work not only produces an efficient CO2‐to‐methanol catalyst, but also opens a new avenue for designing superior catalysts for other consecutive transformations.
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