X-ray crystal structures of three substituted 4,4’-biphenyldiamines, namely, 2,2’,6,6’-tetramethylbenzidine (TMBZ), 2,2’-dimethylbenzidine (DMBZ) and 2,2’-bis(trifluoromethyl)benzidine (BFBZ), were determined. The torsional angles between the two phenyl rings for TMBZ, DMBZ, and BFBZ are phi = 83 degrees, 75 degrees, and 59 degrees, respectively. A structure-property relationship between the three-dimensional configuration of diamine monomers End the corresponding polyimides is discussed.