In the presence of polyethylene glycol (PEG), bimodal mesoporous nanorod gamma-Al2O3 was successfully synthesized via hydrothermal method. The pore structure, crystal parameters and morphology of the alumina can be controlled by PEG. The more PEG can facilely induce the formation of bimodal mesoporous skeletal nanorod structure and lead to the relatively higher crystallinity to the alumina. This novel structure alumina result in the catalysts for hydrodesulfurization (HDS) possessing lower metal-support interaction and higher crystal phase dispersion. The nanorod structure of alumina contributes shorter crystallite length and higher staking degree to the catalysts. Of note is that there is apparently pore confinement effect on the HDS process. The catalysts with bimodal mesoporous structure indicate the higher HDS activity than that of catalyst with mono-modal structure. (c) 2012 Elsevier B.V. All rights reserved.