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A novel Lewis acidic ionic liquid, 1-methyl-3-(4-butylsulfonyl chloride)imidazolium chlorosulfate ([MBClm]SO3Cl), featuring both Lewis acidic anion and cation, was synthesized and demonstrated to be efficient catalyst for dehydration of aldoximes to nitriles.An unexpected reaction induced self-separation was observed when the reaction was carried out in acetonitrile, which could be attributed to the hydrolysis of [MBCIm]SO3Cl to regenerate 1-methyl-3-(4-butylsulfonyl acid)imidazolium hydrosulfate ([MBAlm]HSO4), the Br(o)nsted precursor of [MBCIm]SO3Cl.