In the present study, the effect of varying titanium dioxide (TiO2) nanoparticles on the dielectric, thermal, and corrosion characteristics of PI-based composites prepared by spark plasma sintering was investigated. The results obtained revealed that the TiO2 nanoparticles were uniformly dispersed within the PI matrix. Addition of TiO2 into the neat PI markedly reduced its dielectric constant and electrical conductivity by 72.7% and 82.3%, respectively, as well as enhancing its breakdown strength by 16.7% at 8 wt% TiO2 loading. The nanocomposites depict better thermal stability and heat-resistance index characteristics when compared to the PI. Additionally, the produced nanocomposites exhibit improved corrosion resistance than that of the neat PI. The remarkable improvement in the dielectric, thermal stability, and corrosion resistance of the nanocomposites is achieved by better dispersion of the TiO2 particles in the polymer matrix. The enhancement in properties suggests TiO2/PI-based nanocomposites potential for a variety of applications in electrical insulation, thermal management, and harsh environment.