Glycerol was converted to liquid fuels through a one-pot process catalyzed by mesostructured Ir-Re-W/SiO2. The reaction was performed over 0.4g of catalyst suspended in an aqueous solution of glycerol (4.72 mmol/ml) at 553K under a hydrogen pressure of 6.0 MPa for 50 h. A hydrocarbon-enriched organic phase was self-separated from the aqueous solution after the reaction. The total yield of oil products was greater than 40%, and the selectivity toward hydrocarbons was approximately 90%. The conversion proceeds through a complicated mechanism that involves a C C coupling reaction and hydrodeoxygenation. Doped tungsten oxide species in a silica matrix are active acidic sites for acid-catalyzed dehydration. Supported iridium species are catalytic active sites for hydrodeoxygenation and C C coupling reactions. The evolution of their chemical states during the catalytic process was detected by X-ray photoelectron spectroscopy. Rhenium species are important co-catalysts for iridium species. These active catalytic species work together to achieve the direct conversion of glycerol in aqueous solution to liquid fuels under a hydrogen atmosphere. (C) 2012 Elsevier B.V. All rights reserved.