Egg-shell like Ni-based catalyst was prepared on a porous hollow silica (PHS) support to synthesize methanol from CO hydrogenation. It was found from Transmission Electron Microscope (TEM) that Ni particles with a size of 9-11 nm were loaded on PHS to obtain the egg-shell catalysts. X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) analyses indicated that the active site of the catalysts was metallic Ni, which would not be oxidized during the reaction. When the as-prepared Ni/SiO2 egg-shell catalyst was used for CO hydrogenation at 220 degrees C and 2.0 MPa, the conversion of CO and selectivity to methanol were about 69.5 mol% and 92 mol%, respectively, showing higher activity and selectivity than conventional catalysts. The thermodynamic analysis of CO hydrogenation for methanol synthesis indicated that the conversion of CO is 69.5 mol% under these conditions. (c) 2006 Elsevier B.V All rights reserved.