Electrochemical reduction of carbon dioxide (CO2) to fuels and chemicals provides a promising solution for renewable energy storage and utilization. Among the many possible reaction pathways, CO2conversion to carbon monoxide (CO) is the first step in the synthesis of more complex carbon‐based fuels and feedstocks, and holds great significance for the chemical industry. Herein, recent advances in heterogeneous catalysts for selective CO evolution from electrochemical reduction of CO2are described. With Au catalysts as a paradigm, principles for catalyst design including size, morphology, and grain boundary densities tuning, surface modifications, as well as metal‐support interaction are comprehensively summarized, which shed light on the development of other transition metal catalysts targeting efficient CO2‐to‐CO conversion. In addition, recently emerged novel materials including transition metal single‐atom catalysts, which present significantly different catalytic behaviors compared to their bulk counterparts and thus open up many unexpected opportunities, are summarized. Furthermore, the technical aspects with respect to large‐scale production of CO are presented, focusing on the full‐cell design and implementation. Finally, short comments related to the future direction of real‐word CO2electrolysis for CO supply are provided in terms of catalyst optimization and technical breakthrough.