A series of MoO3/SiO2 catalysts was prepared by an impregnation method with Mo loadings ranging from 1 to 50 wt%. The original and calcined samples at 400 degrees C were characterized by thermogravimetry (TG), differential thermogravimetry (DTG), differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier transform infra-red (FTIR) spectroscopy, and nitrogen adsorption measurements. The surface acidity and basicity of the catalysts were investigated by the dehydration-dehydrogenation of isopropanol and the chemisorption of pyridine. The catalytic esterification of acetic acid with ethanol was carried out at 220 degrees C in a conventional fixed-bed reactor at 1 atm using air as a carrier gas. The results clearly revealed that silica-molybdena catalysts were active and selective towards the formation of ethyl acetate. Moreover, the catalyst containing 20 wt% MoO3 was the most active and selective one. The results emphasize the importance of the surface acid sites together with the specific surface area of the prepared catalyst, towards ester formation. (c) 2005 Society of Chemical Industry