AbstractTransition to electrified transportation demands advanced power electronic components with the capability to improve range, reliability, and cost of ownership to accelerate mass market adoption. Thus, improvement in the current designs, manufacturing processes, materials, and components capable of providing reliable and efficient operation at higher temperatures play important roles in meeting future needs. To address these challenges, this article focuses on novel dielectric materials designed to reduce the volume of the most important and bulky component of a power electronic system, a capacitor. A new composite dielectric material was developed by integrating the positive attributes of both polymer and ceramic capacitors to overcome the challenges of state‐of‐the‐art dielectric materials. The developed composite properties have been evaluated and showed promising results, achieving a dielectric constant of 250 at 100 Hz, 25°C, unseen in current literature. Additionally, these materials can function at high temperatures (>150°C) with good breakdown strength, providing promising working conditions for capacitors, especially in electric vehicle applications.Highlights Dielectric composites were synthesized from calcium copper titanate and polyimide. A dispersive agent showed promise in achieving a homogenous, stable mixture. Composites were prepared using tape casting. A dielectric constant of 250 was achieved at 100 Hz, 25°C. At elevated temperature, the dielectric constant increased to over 700%.