Novel egg-shell structured monometallic Pd/SiO2 and bimetallic Ca-Pd/SiO2 catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl2 and Ca(NO3)(2)center dot 4H(2)O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO2 samples and the Pd particle size in Ca-Pd/SiO2 was smaller than that in Pd/SiO2 since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d(5/2) binding energies of Pd/SiO2 and Ca-Pd/SiO2 were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO2 and to both oxygen and Ca in Ca-Pd/SiO2. The activity of Ca-Pd/SiO2 egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol(CO) mol(-1) (Pd) s(-1) and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support. (c) 2006 Elsevier B.V. All rights reserved.