Porous polyimide hybrid films with ultralow dielectric constant and dissipation loss were synthesized during chemical imidization and rapid evaporation of polymer solutions. Polyimide (PI) of bis(4-aminophenyl)-1,4-diisopropylbenzene (BISP) and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) were synthesized in N-methylpyrrolidinone (NMP) to yield the corresponding poly(amic acid)s (PAA)s, which were then chemically imidized. To reduce the dielectric properties of the porous PI films, amine-functionalized, surface-modified hollow silica nanoparticles (AHNS) with various sizes from 100 nm to 1 μm, prepared via sol-gel process, were added with PAA at 3, 5, or 10 % weight content, followed by chemical imidization to produce the porous PI/AHNS films. To avoid the high-volume shrinkage of wet gels and maintain the high porosity of the PI with low polarizability, AHNS nanoparticles were added to the porous structure of the PI xerogels as a physical crosslinker. The polyimide hybrid film with 10 nm AHNS nanoparticles at 10 % weight content showed a dielectric constant of 1.151 and a dissipation rate of 0.001 at a frequency of 10 GHz.