<p>Cu-based catalysts are promising candidates for the electrocatalytic reduction of CO₂ (CO₂RR) toward multicarbon products. However, designing suitable active sites in Cu metal-organic frameworks (MOFs) remains a critical challenge, owing to their inherent structural instability during CO₂RR and the difficulty in simultaneously optimizing morphology and electronic structure. In this work, we report a facile one-pot synthesis of gadolinium-doped HKUST (Gd_<i>x</i>/HKUST), integrating morphological and electronic modulation to selectively electroreduce CO₂ to ethanol. The optimized Gd_0.25/HKUST catalyst exhibits a unique wheat-ear-like morphology (thus conducive to CO₂ adsorption and accessibility) and a Gd-induced valence state transition from Cu⁺ to Cu⁰, as corroborated by a suite of physicochemical characterizations. Electrochemical evaluation at −1.0 V presents a high Faradaic efficiency of 54.5% for ethanol, surpassing pristine HKUST, along with stability exceeding 60 h. <i>In situ</i> spectroscopic analyses indicates the rapid consumption of *CO species, followed by the subsequent hydrogenation of *CO to form *CHO and the further generation of *OC₂H₅ on the Gd_0.25/HKUST catalyst. Theoretical studies reveal that Cu-Gd bimetallic synergy lowers the energy barrier for *CHO hydrogenation, thereby facilitating C-C coupling. This work highlights a dual-strategy approach integrating morphological and electronic modifications in MOF-based catalysts, thus advancing the rational design of efficient CO₂-to-C₂₊ conversion systems.</p>