The study is dedicated to finding optimal reaction conditions for the introduction of 4-nitro-and 4-aminophenyl substituents into the structure of azacrown ethers with a varied ratio of oxygen to nitrogen heteroatoms. The synthetic procedure is proposed for the synthesis of 4-nitroaryl derivatives of crown ethers. This method is remarkably simple, has easy work-up and affords the formation solely of the monoarylation product.