Methanol synthesis from sulfur-containing syngas over Pd/CeO2 catalyst has been investigated in this study, the characterization methods like X-ray powder diffraction (XRD), X-ray fluorescence (XRF), X-ray photoelectron spectroscopy (XPS) and pulse experiments has also been carried out for elucidating sulfurtolerant mechanism of Pd/CeO2 catalyst. The results show that methanol synthesis from sulfur-containing syngas exhibit stable reaction activity over Pd/CeO2, It Was indicated from characterization analysis that the sulfur-tolerance of Pd/CeO2 was due to the capability of CeO2 for transforming H2S to SOx. Thus, Pd active sites for methanol synthesis were protected from sulfur poisoning, which was the main deactivation reason of Pd/Al2O3 catalysts. A sulfur-tolerant model of Pd/CeO2 catalyst for syngas to methanol was proposed according to the reaction performance and characterization results, which might be expanded to other sulfur-containing feed gas reaction systems over metal/ceria-type oxides. (C) 2009 Elsevier B.V. All rights reserved.