Abstract Silica-supported Co–Pd catalysts were prepared by co-impregnation using 2wt% Pd and two different cobalt loadings: 2wt% (2Co–2Pd) and 10wt% (10Co–2Pd). They were characterized by ICP-OES, H2-TPR, in situ XRD, DRIFTS, and activity/selectivity in CO hydrogenation. Activity/selectivity studies showed that the 10Co–2Pd catalyst is more active for CO hydrogenation with high selectivity toward hydrocarbons, while 2Co–2Pd catalyst shows higher selectivity toward oxygenates, but considerably lower overall activity. DRIFTS studies for 10Co–2Pd catalyst at 230°C indicated that sites at which CO adsorbs linearly are the main active sites for CO hydrogenation, which leads toward formation of hydrocarbons. On the other hand, the bridged sites were found to be the main active sites for 2Co–2Pd catalyst, which leads to increased selectivity toward oxygenated compounds. The hydrogenation of CO adsorbed on these bridge sites was found to be much slower, explaining the low activity of this catalyst.