Several highly soluble polyimides were synthesized from various aromatic tetracarboxylic dianhydrides and an aromatic diamine containing tert-butyl pendent groups [4,4 ' -methylenebis(2-tert-butylaniline)]. All the polyimides showed excellent solubility in common solvents such as chloroform, tetrahydrofuran, and dioxane at room temperature. The number-average molecular weight ranged from 3.6 X 10(4) to 1.3 X 10(5) according to gel permeation chromatography relative to a polystyrene standard, and the polydispersity index was between 1.9 and 2.5. The glass-transition temperatures of the resulting polyimides ranged from 213 to 325 degreesC, as measured by differential scanning calorimetry, and little weight loss was observed up to 450 degreesC in N, by thermogravimetric analysis. These experimental data indicated that the tert-butyl pendent groups reduced the interactions among polymer chains to improve their solubility in organic solvents without the loss of thermal stability. Transparent and flexible films of these polyimides were obtained via casting from solution.