A novel tert-butyl-containing dianhydride was prepared from readily available reagents. It was reacted with various aromatic diamines to prepare a set of polyimides containing tert-butyl pendent groups. The resulting polyimides exhibit high molecular weights (high inherent viscosity), and a combination of desirable properties, such as good solubility in aprotic amide solvents and cresols, high glass transition temperatures (up to 320degreesC), high thermal resistance, film-forming capability and good mechanical properties.