A series of novel polyimides was prepared from various diamines (with bisphenol units) and various aromatic tetracarboxylic dianhydrides via a two‐step (thermal imidization) method. The monomers and polymers were produced in high yields. The benzophenone series exhibited better solubility than the pyromellitic series and, especially, those with the alkyl (methyl)‐substituted ring exhibited good solubility and could be readily dissolved in polar aprotic solvents such as dimethylformamide and N,N′dimethylacetamide. The glass transition temperatures of all polyimides were found to be 235–322 and 223–332°C, respectively, by DSC and dynamic mechanical analysis. Thermogravimetric analyses indicated that the polymers were fairly stable up to 482–617°C (10 wt % loss in N2) and 480–610°C (10 wt % loss in air). Wide‐angle X‐ray diffractograms revealed that most polyimides were predominantly amorphous. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 945–952, 2003