The deoxydehydration of polyols to alkenes is one of the important methods for the conversion of biomass-based platform molecules to useful chemicals and liquid fuels. A new imidazolinium perrhenate catalytic system for the deoxydehydration of vicinal diols to alkenes was reported. The reaction conditions, including reductants, solvents and imidazolinium cations were investigated. The best result was obtained with 3 equiv. of 3-octanol as the reductant in chlorobenzene at 180℃ under argon atmosphere, affording the 1-tetradecene product in 85% yield after 24 h. The catalyst shows moderate activity for several vicinal diols and can be reused after recoverd.