A rapid method for the selective cleavage of aryl methyl ether in the lithium chloride-N,N-dimethylfortnamide (LiCl-DMF) system under microwave irradiation has been, developed. Effects of substituent, metal salt and solvent on the activity and selectivity in the cleavage reaction have been investigated. It is found that microwave significantly improves the reaction yield and the selectivity of demethylation for electron deficient aromatic methyl ethers. The catalytic mechanism of demethylation by LiCl salt is proposed. (c) 2007 Published by Elsevier B.V.