The iron(ii) divalent ion conducting electrolyte matrix has prepared in different ratio of glycerol and polyvinylpyrrolidone (PVP) blend by impregnating ferrous sulfate crystals. The complexation of the polymer mixing transformed into gel format, the composition has been analyzed by the Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) characterization techniques. The amorphous nature of electrolyte to support the ion conduction has been revealed by XRD as well as the FTIR results confirmed the glycerol and PVP interaction feasibility with the ferrous sulfate mixing. Further overall electrical conduction and dielectric behaviors has been explored through Electrochemical impedance spectroscopy (EIS) within the frequency range of 1Hz to 1GHz, the complex permittivity analysis is employed in order to verify dynamic modes of ion conduction symptoms including short to long range ion hopping in polymer backbone segmental movement along with dielectric dissipation level. The studies provide us a feasible direction to utilize this new iron assisted dielectric matrix with eco friendly glycerol composition to be applicable for iron based capacitor-battery hybrid energy storage system.