A developed polyvinyl alcohol/polyethylene glycol (PVA/PEG) blend containing different concentrations of graphene oxide GO (PVA/PEG-GO) as dialectic materials for energy storage devices was studied. 80 wt% of PVA/ 20 wt% of PEG were doped with 0.5, 1.5, and 3 wt% of graphene oxide and prepared using the solution casting technique. The electrical properties, the dielectric constant (𝜺'), dielectric loss (𝜺"), and ac conductivity (σ_ac), in a wide range of frequencies, were extensively investigated. The GO strongly enhanced the dielectric constant (energy storage) of the produced PVA/PEG blend, while a little variation was observed in dielectric loss (energy loss). A higher frequency shift was observed in the loss tangent peak, reflecting an augmentation in the mobility speed of the ions, causing a longer relaxation time. In response to the electric field, the charge carriers' mobility has a short range. The addition of GO caused a reduction in the semicircle diameter of a Cole-Cole profile. The ac conductivity was found to obey the power law, and the ionic conduction dominates the conductivity in all the studied frequency ranges. The produced PVA/PEG-GO blends had significant energy storage characteristics, making them an excellent choice for dielectric materials in energy storage devices.