BACKGROUNDConverting the syngas‐derived dimethyl oxalate (DMO) intermediate to versatile simple diols (ethylene glycol, EG) has been deemed as a promising chemical synthesis technology, owing to the cheap, widely available raw materials. Nonetheless, finding the optimal catalyst for this route is still challenging. In this work, copper (Cu)‐doped cobalt/zinc oxide (Co/ZnO)‐based CoCu/ZnO catalysts for DMO selective hydrogenation to EG were successfully synthesized by the oxalic co‐precipitation method.RESULTSThe Cu content shows significant influence on Co dispersion and chemical features, further determining the resultant structural and morphology properties of the as‐prepared samples. For DMO gas‐phase hydrogenation, the CoCu20/ZnO catalyst prepared in presence of the 20.0 wt% Cu additive exhibited 100.0% DMO conversion and 93.0% EG yield, superior to that of the other catalysts due to adequate active Co0 sites released adjacent to the Cu species. Moreover, the CoCu/ZnO catalyst showed outstanding thermal stability in DMO‐selective hydrogenation for >200 h.CONCLUSIONSThe H2 activation ability and capability of the surface Co species depends critically on the Cu content, further regulating the reaction pathways of the DMO hydrogenation. © 2023 Society of Chemical Industry (SCI).