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A series of ionic liquids were used as a co-solvent in the reaction of one-pot synthesis of phenols from aromatics and hydroxylamine. Then an eco-friendly catalytic system, i.e., [HSO3-bmi [CF3SO3]-H2O-HAc media with (NH4)6Mo7O24·4H2O catalyst, was designed for the reaction. The results showed that aromatics were successfully hydroxylated to give the corresponding phenols. Recycling experiments suggested that the catalytic system was stable enough to be recycled.