Abstract: Silica was treated with trimethylchlorosilane before using as the supports for Rh-Mn-Li catalysts in CO hydrogenation to C₂ oxygenates. The catalysts were characterized by infrared spectroscopy, N₂ adsorption-desorption, C content measurements, transmission electron microscopy, H₂ temperature programmed reduction, and temperature programmed surface reaction. The results showed that the silanization degree has little effect on the textural properties of silica. The mean Rh particle size (about 3nm), CO adsorption state on Rh and reducibility of Rh supported on silica remain unchanged by the silanization of silica support. However, with an increase of the silanization degree of silica, the ability of Rh to dissociate CO is improved, which can enhance the catalytic activity of Rh-Mn-Li/SiO₂ in CO hydrogenation but has little influence on the selectivity towards C₂ oxygenates.