CoMn model catalysts were prepared by co-precipitation and evaluated for higher alcohol synthesis (HAS) via syngas. The selectivity to oxygenates (mainly alcohols and aldehydes) was found to be higher than 20 C% for the Na-promoted CoMn catalyst. Among the oxygenates, C2+ and C6+ fractions accounted for > 90 wt% and similar to 50 wt%, respectively. Metallic Co-0 particles and MnCO3 were found in both Na-promoted and unpromoted CoMn catalysts after the reaction, whereas Co2C nanoparticles could only be observed in the spent Na-promoted catalyst. The addition of Na benefited the carbonization of cobalt and increased the selectivity to oxygenates and CO2. Our studies thus suggested that Co/Co2C were the bifunctional dual-sites for the oxygenates formation over the Na-promoted CoMn catalyst, where Co catalyzed CO dissociation and chain propagation, while Co2C was responsible for CO non-dissociative activation and subsequent insertion. In addition, the sole Co2C nanoparticles with certain exposed facets may also act as another kind of active dual-sites for oxygenates formation.