Most polyolefins that are used for dielectric materials exhibit a low dielectric constant and operating temperatures up to 70 degrees C. Polyimides offer a means to a higher dielectric constant material by the introduction of a polar group in the polymer backbone and are thermally stable at temperatures exceeding 250 degrees C. A common dianhydride, pyromellitic dianhydride (PMDA), is reacted with various short-chain diamines to produce polymers with high imide density. Homopolymers and copolymers synthesized had dielectric constants ranging from 3.96 to 6.57. These materials exhibit a dielectric constant twice that of biaxially oriented polypropylene and therefore a twofold increase in capacitance as well as maintaining low dissipation factors that are acceptable for this application. The experimental dielectric constants of these materials are also compared to density functional theory calculations and exhibit a close relationship. (C) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1276-1280, 2013