Abstract We have developed an efficient and inexpensive bimetallic catalyst FeCl 3, CuO, and rac-BINOL that could promote N, O-arylation of aliphatic, arylamines, and phenols. The cross-coupling reaction conditions have high tolerance of various functional groups. This versatile and efficient iron/copper-cocatalyst can widely be used in the synthesis of the compounds containing (aryl) CN or (aryl) CO (aryl) bond.