Copper sulfate catalyzed an efficient, inexpensive, and environment-friendly protocol that has been developed forN-arylation of amines with 1,3-cyclohexadione-derived aryliodonium ylides in water as a green solvent. Aromatic primary amines substituted with electron-donating as well as electron-withdrawing groups on the aryl ring reacted smoothly with iodonium ylides to give the corresponding diarylamines with good to excellent yields. Also, secondary amines underwentN-arylation to deliver tertiary amines with moderate yields.