Natural rubber (NR) nanocomposites have been prepared with hydroxylated barium titanate filler (BaTiO3-OH), employing emulsion polymerization followed by vulcanization process. The addition of barium titanate, a compound with high dielectric permittivity, was envisaged to increase the insulating properties of NR films, thereby reducing the electrical stress and the possibility of undesired arcing on their surfaces. The content of perovskite particles greatly affected both, the mechanical and the electrical properties, of the vulcanized films. It was observed that the optimum functionalized nanoparticle concentration is around 0.25–0.50 phr, range in which the elongation of break was maintained between 874–935% and the tensile strength was between 4.40–4.80 MPa; whereas the dielectric permittivity (¿') is slightly lower than the pristine NR or the NR compounded with high content of BaTiO3 nanoparticles. The dielectric study revealed the presence of two dielectric relaxation modes: (i) glass to rubber transition (a-relaxation) and (ii) interfacial polarization (IP), known as Maxwell-Wagner-Sillars (MWS) polarization. The comparison between small concentrations of non-functionalized and functionalized BaTiO3 inside NR polymeric films lead to the conclusion that the dielectric breakdown strength is high for non-functionalized fillers, supposedly due to less IP polarization phenomena.