Emerging as a new class of two‐dimensional materials with atomically thin layers, MBenes have great potential for many important applications such as energy storage and electrocatalysis. Toward mitigating carbon footprint, there has been increasing interest in CO 2 /CO conversion on MBenes, but mostly focused on C 1 products. C 2+ chemicals generally possess higher energy densities and wider applications than C 1 counterparts. However, C–C coupling is technically challenging because of high energy requirement and currently few catalysts are suited for this process. Here, we explore electrochemical CO reduction reaction to C 2 chemicals on Mo 2 B 2 O 2 MBene via density‐functional theory calculations. Remarkably, the most favorable CO–COH coupling is revealed to be a spontaneous and barrierless process, making Mo 2 B 2 O 2 an efficient catalyst for C–C coupling. Among C 1 and C 2 chemicals, ethanol is predicted to be the primary product. Furthermore, by charge and bond analysis, it is unraveled that there exist significantly more unbonded electrons in the C atom of intermediate *COH than other C 1 intermediates, which is responsible for the facile C–C coupling. From an atomic scale, this work provides microscopic insight into C–C coupling process and suggests Mo 2 B 2 O 2 a promising catalyst for electrochemical CO reduction to C 2 chemicals.