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The alkylation of benzene with 1-hexene has been investigated in different triethylamine hydrochloride-ferric chloride (Et3NHCl-FeCl3) and triethylamine hydrochloride-aluminium chloride (Et3NHCl-AlCl3) ionic liquids. Both high catalyst activity and monoalkylation selectivity were observed for these two type of ionic liquids. Systems prepared by modification with HCl in Et3NHCl-FeCl3ionic liquids prove to be very suitable solvents and catalysts for the reaction. When employing Et3NHCl-AlCl3ionic liquids as catalysts, the reaction takes place in biphasic mode with facile catalyst separation and catalyst recycling.