A new dianhydride containing pendent phenyl group and alicyclic unit was prepared by a bis-Diels-Alder reaction of 1,4-diphenyl-2,3,5,6-tetrakis(bromomethyl)benzene with maleic anhydride, and polymerized with various aromatic diamines in one step at high temperature in NMP. Polymers were soluble in NMP and their inherent viscosities were in the 0.29similar to0.47 dL/g range. Polyimides properties were investigated and discussed in terms of the chain structure resulting from the incorporation of different diamines.