Polymer dielectrics with high dielectric constant, low dielectric loss, high breakdown strength, and high temperature capability are attractive for applications such as capacitive energy-storage. Commercially available polymer dielectrics such as biaxially oriented polypropylene (BOPP), poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), polycarbonate (PC), and poly(vinylidene) fluoride (PVDF) can be just operated below 200°C. Great effort has been put into exploring high temperature polymer dielectrics to fulfill the demand of high temperature applications, such as the aerospace and military power supply. In this study, a series of polyimides containing bipyridine units with good dielectric performance and high temperature capability were prepared by using a newly synthesized diamine monomer, (5,5′-bis [(4-amino) phenoxy]-2,2′-bipyridine (BPBPA)). These polyimides possessed high dielectric constant of the as-synthesized polyimides can be up to7.2, the dielectric loss was <0.04, and the energy density was up to 2.77J/cm3. Furthermore, the polyimides exhibited high glass transition temperature (Tg) of 275–320°C and tensile strengths of 175–221MPa. These obtained polyimides promise potential applications in high temperature flexible polymer film capacitor operated at high temperature.