Flower like radial zinc oxide (RZnO) was prepared by using a facile solvothermal method and used to prepare poly(vinylidene fluoride) (PVDF) based nanocomposites. Structural informations of the samples are analyzed by X-ray diffraction and correlated with high resolution transmission electron microscopy along with high annular angular dark field scanning transmission electron microscopy (HAADF-STEM). For the first time, stability studies are carried out by solvent relaxation nuclear magnetic resonance experiments. Dielectric studies of the PVDF and PVDF-RZnO nanocomposites are reported over the wide range of frequency (0.01 Hz-1 MHz) and temperature (25-90 degrees C). Dielectric property of the PVDF-RZnO nanocomposites was significantly improved wrt filler percentage in PVDF. Unique negative permittivity was observed in the composites having higher filler content (>40 wt%) typically at low frequencies. First time, it is observed that the higher RZnO content in PVDF results the formation of pseudo conducting network and hence improved the electromagnetic shielding efficiency (85%) than PVDF and PVDF-commercial ZnO composites. (C) 2015 Elsevier B.V. All rights reserved.