Abstract An inexpensive and efficient catalyst system for synthesis of aryl ethers has been developed by using 20 mol% CuI as the catalyst, 30 mol% dimethylaminomethylphosphonic acid derivatives as the new ligands, K 2 CO 3 as the base and toluene as the solvent. This is the first example using aminophosphonates as the ligands for Ullmann ether coupling reaction.