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Three novel alkoxyl-functionalized ionic liquids (ILs), 1-(3-triethoxysiyl propyl)-3-methyl imidazolium tetrafluoroborate (TESPMIM[BF4]), 1-(3-triethoxysiyl propyl)-3-methyl imidazolium hexafluorophosphate (TESPMIM[PF6]) and 1-(3-triethoxysiyl propyl)-3-methyl imidazolium bis(trifluoromethanesulfony)imide (TESPMIM[N(SO2CF3)2]) were synthesized and used as selective coating materials to prepare chemically bonded IL-based organic-inorganic hybrid solid phase microextraction (SPME) fibers by sol-gel technology.The possible mechanism of the sol-gel process was proposed, and the successful binding of ILs to the sol-gel substrate was confirmed by FT-IR spectroscopy.