The effect of calcination temperature of the monodispersed SiO2 synthesized by the Stober method on the catalytic performance of Rh-Mn-Li/SiO2 for CO hydrogenation to C-2 oxygenates was investigated. The means of N-2 adsorption-desorption, in-situ FT-IR, H-2-TPD, H-2-TPR, CO-TPD, and TPSR were used to characterize the physico-chemical properties of SiO2 supports and the corresponding Rh-Mn-Li/SiO2 catalysts. The results showed that the amount of surface Si-OH groups on SiO2 affects the Rh dispersion and Rh-Mn interaction. The increase in the number of Si-OH groups on the SiO2 was favorable for the Rh dispersion and CO adsorption, further enhanced the activity of the catalyst. In addition, an appropriate amount of surface Si-OH groups on the SiO2 calcined at 350 degrees C can gain a moderate Rh-Mn interaction. This interaction is conducive to achieve the right hydrogenation ability, which is favorable for the CO insertion into metal-CHx band, and ultimately increases the selectivity of C-2 oxygenates. (C) 2012 Elsevier B.V. All rights reserved.