A new dianhydride containing phenoxy groups and alicyclic unit was prepared by a bis-Diels-Alder reaction of 1,4-diphenoxy-2,3,5,6-tetrakis(bromomethyl)benzene with maleic anhydride, and polymerized with various aromatic diamines in one step at high temperature in NMP. All the polymers had good solubility toward polar solvents and their inherent viscosities were in the range of 0.31 similar to0.53dL/g. Polyimides properties were investigated and discussed in terms of the chain structures resulting from the incorporation of different diamines. All the polyimides were thermostable up to 475 degreesC with 10% weight loss and in DSC thermograms the polymers exhibited T(g)s between 249 and 317 degreesC.