Low‐dielectric‐constant aromatics, homopolyimide and copolyimide, were introduced. Homopolyimides were prepared by pyromellitic dianhydride (PMDA) as an anhydride monomer and 4,4′‐oxydianiline (ODA), 2,2‐bis[4‐(4‐aminephenoxy)phenyl]propane, 1,4‐bis(4‐aminophenoxy)benzene, or 1,3‐bis(4‐aminophenoxy)benzene as an amine monomer. The copolyimides were prepared with PMDA as an anhydride monomer, ODA as an amine monomer with the addition of 2,2‐bis[4‐(4‐aminephenoxy)phenyl]propane, 1,4‐bis(4‐aminophenoxy)benzene, or 1,3‐bis(4‐aminophenoxy)benzene as another amine monomer. The polyimides were well characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, thermomechanical analysis, dielectric measurements, and tensile testing. The homopolyimide and copolyimides showed lower dielectric constants than the homopolyimide formed by ODA and PMDA. The results also indicate that the interchain distance, the quantities of phenyl ether, and the position of the substitute are factors that not only affected the thermal performance of polyimide by improving the molecular flexibility but also reduced the dielectric constant of polyimide by increasing the free volume of the molecular chain and decreasing the polarization points per unit volume. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47405.