Abstract: Two new azoxybisbenzocrown ethers were synthesized. Preparative method of azo-xybisbenzo-15-crown-5 has been improved with the yield up to 65.3%. It was obser-ved that the degree of dissociation of electron-transfer agent plays an important role in product yield. The results were interpreted in terms of solvent polarity.Photo- and thermo-isomerization of azoxybisbenzocrown ethers have been studied preliminarily.