Polymer nanocomposites exhibit unique effective properties that do not follow conventional effective media approaches. The nanoparticle-polymer interphase has been shown to strongly influence the nanocomposites behavior due to its significant volume when the particles are nano-sized, affording an opportunity to tune the dielectric response of the resulting nanocomposite. In this study, we investigate the effects of TiO2 nanoparticles on the electrical properties and the charges distribution and transport in polydimethylsiloxane (PDMS) nanocomposites. Impedance spectroscopy shows suppression of interfacial Maxwell-Wagner-Sillars (MWS) polarization accompanied by a reduction in the low frequency dielectric permittivity and loss at high temperatures in the presence of the TiO2 nanoparticles. Thermally stimulated discharge current measurements confirm that the suppression of the interfacial polarization relaxations happens by redistributing or depleting the charges through the composite and hindering their mobility, potentially resulting in lower electrical conduction and higher breakdown strength. Although the model materials investigated here are TiO2 nanoparticles and Sylgard 184 PDMS, our findings can be extended to other nanoparticulate-filled elastomer composites to design lightweight dielectrics, actuators and sensors with improved capabilities.