Graphene oxide/polyvinyl alcohol (GO/PVA) composites have been developed using facile colloidal processing technique to form a super dielectric spacer of 10(6) order. The dielectric characteristics of GO/PVA composite were investigated at a frequency range from 20 Hz to 1 M Hz. The electrical analysis showed a complex interaction that is quite different than Debye but could be explained using Bruggeman and Maxwell-Garnett assumptions in the high-frequency range and Percolation theory in the low range. Due to the ageing effect and the observed high imaginary part, an investigation of GO film dielectric properties were investigated. The results incorporate a crucial role of water contents on corresponding GO and GO/PVA electromagnetic interaction besides the well-established functional group's theory. Transmission electron microscopy, X-ray diffraction, dispersive Raman, potentiostat/galvanostat and LCR meter were utilized to perform microscopic, structure and electrical characterizations.