The multi‐carbon (C2+) alcohols produced by electrochemical CO2 reduction, such as ethanol and n‐propanol, are considered as indispensable liquid energy carriers. In most C–C coupling cases, however, the concomitant gaseous C2H4 product results in the low selectivity of C2+ alcohols. Here, we report rational construction of mesostructured CuO electrocatalysts, specifically mesoporous CuO (m‐CuO) and cylindrical CuO (c‐CuO), enables selective distribution of C2+ products. The m‐CuO and c‐CuO showed similar selectivity towards total C2+ products (≥76%), but the corresponding predominant products were C2+ alcohols (55%) and C2H4 (52%), respectively. The ordered mesostructure not only induced the surface hydrophobicity, but selectively tailored the adsorption configuration of *CO intermediate: m‐CuO preferred bridged adsorption, whereas c‐CuO favored top adsorption as revealed by in situ spectroscopies. Computational calculations unraveled that bridged *CO adsorbate is prone to deep protonation into *OCH3 intermediate, thus accelerating the coupling of *CO and *OCH3 intermediates to generate C2+ alcohols; by contrast, top *CO adsorbate is apt to undergo the favorable conventional C–C coupling process to produce C2H4. This work illustrates selective C2+ products distribution via mesostructure manipulation, and paves new path into the design of efficient electrocatalysts with tunable adsorption configuration of key intermediates for targeted products.