Conversion of a series of lignin β-O-4 model compounds 2-aryloxy-1-arylethanols and organosolv lignin to aromatic chemicals over methyltrioxorhenium (MTO) in ionic liquids without any oxidant and reducing agent under mild conditions was developed. Microwave irradiation accelerates the cleavage of aryl ether bonds and shortens the reaction time to 2 min.