A new aromatic tetracarboxylic dianhydride having a crank and twisted noncoplannar structure, 2,2＇-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with biphenyl-2,2＇-diol, followed by hydrolysis and cyclodehydration. The biphenyl-2,2＇-diyl-containing aromatic polyimides having inherent viscosities up to 0.66 dL/g were obtained by the conventional two-step procedure starting from the dianhydride monomer and various aromatic diamines. Most of the polyimides were readily soluble in amide-type solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The aromatic polyimides had glass transition temperatures in the range of 205-242 degrees C, and began to lose weight around 415 degrees C, with 10% weight loss being recorded at about 500 degrees C in air.