A soluble perylene monoanhydride diester has been designed and synthesized. It was successfully utilized as an efficient intermediate for the synthesis of the first unsymmetric perylene tetracarboxylic tetraester and a series of unsymmetric perylene diester monoimides in good to excellent yields. Its application in synthesis of unsymmetric perylene diimides was also demonstrated. Availability of such a versatile intermediate would enable the convenient integration of perylene tetracarboxylic tetraesters and perylene biester monoimides into intricate functional molecular systems.