Polyimides (PIs) are highly desirable materials due to their excellent physical, chemical properties, and widespread applications. In this article, a new PI containing bipyrimidine units was prepared from a newly synthesized 5,5′-bis[(4-amino) phenoxy]-2,2′-bipyrimidine and 3‚3′‚4‚4′-biphenyltetracarboxylic dianhydride via a two-step method. The as-synthesized PI not only showed high thermal stability and excellent mechanical properties, but also possessed high dielectric constant (7.1, 100 Hz) and low dielectric loss (below 0.04) in a wide frequency range from 100 Hz to 105 Hz. The obtained PI promises potential applications in electronic products. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40828.