Abstract Efficient electrochemical conversion of CO 2 to multi‐carbon (C 2+ ) products remains significant challenges, particularly under broad pH ranges and high‐current‐density conditions. Herein, we report ampere‐level CO 2 ‐to‐C 2+ electroreduction with exceptional efficiency across a wide pH range using ytterbium‐doped CuO x catalysts. The catalyst achieves Faradaic efficiency of 87 ± 2%, 77 ± 1%, and 78 ± 1% under alkaline, neutral, and acidic conditions, respectively. Electrochemical in situ infrared spectroscopy and Raman spectroscopy reveal that Yb‐stabilizing Cu + species and enriching *CO on Cu terrace sites are two critical factors for enhancing C─C coupling. This work not only develops a highly efficient electrocatalysts for sustainable C 2+ production, but also establishes a doping strategy for stabilizing active sites and optimizing *CO adsorption configurations.