Hybrid polymer nanocomposites (HPNCs) are innovative multifunctional materials, which are developed and intensively studied for their uses in the rapid evolution of flexible and lightweight device technologies. Accordingly, to contribute in this area, thermal properties of the crystal phases and the broadband radio frequencies dielectric dispersion and relaxation behaviour of the HPNC films based on poly(vinylidene fluoride) (PVDF)/poly(ethylene oxide) (PEO)/silica (SiO2) are formulated and studied by employing differential scanning calorimeter (DSC) and impedance/material analyzer (IMA). DSC thermograms of these semicrystalline HPNCs explained the wide range alteration in the crystals melting temperature of PVDF (153–167 °C) and PEO (59–72 °C) and the total degree of crystallinity (4–87%) with varying compositional ratio over the entire range of the PVDF/PEO blend host matrix and the dispersed amount of amorphous SiO2 nanomaterial up to 15 wt%. The dielectric dispersion behaviour of these HPNCs, at 20 °C, confirmed a non-linear decrease in permittivity with the increase of applied radio wave electric field frequency from 1 MHz to 1 GHz, which lies in the range of 6 to 2. At a fixed frequency, dielectric permittivity values exhibited an uneven variation with the increase of SiO2 amount and also the modification in the composition of polymer blend matrix in these composites. The analysis of dielectric loss spectra and relaxation processes revealed that these are low loss dielectrics and the presence of SiO2 nanoparticles in the polymer blend matrix impedes the chain segmental dynamics and the dipole reorientation. The electrical conductivity of these HPNCs enhanced in the range of 10−8 to 10−4 S/cm with the increase in frequency but it changed anomalously when the constituent amounts of the formulated composites are varied. The polymer crystals thermal properties and the dielectric and electrical conductivity dispersion behaviour of these materials are demonstrated with the consideration of polymer-polymer and polymer-nanoparticle hybrid interfaces and interactions. The experimental results evidenced the behaviour of PVDF/PEO/SiO2 films as tunable nanodielectrics with their compositions and could be used as insulator and dielectric substrate materials in the advances of flexible radioelectronics and energy storage devices.