In this work, Graphene Oxide (GO) reinforced novel polymer composites comprising of poly (4-styrenesulfonic acid) (PSSA) and polyvinyl alcohol (PVA) blend matrix have been developed using colloidal processing technique. The properties and the structure of prepared composites were investigated using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), UV-vis spectroscopy (UV), Thermogravimetric analysis (TGA), Polarized optical microscopy (POM), Scanning electron microscopy (SEM) and Atomic force microscopy (AFM). The FTIR and Raman spectroscopy analysis indicate the strong interfacial interaction between GO and PSSA/PVA blend matrix. The XRD and SEM analysis confirm that GO was fully exfoliated into individual graphene sheets and dispersed homogeneously within the polymer matrix. The effective reinforcement of GO into PSSA/PVA blend matrix has resulted in the enhancement of dielectric constant. The dielectric constant has increased from 82.67 (50 Hz, 150 degrees C) for PSSA/PVA (50/50) blend to 297.91 (50 Hz, 150 degrees C) for PSSA/PVA/GO composites with 3 wt % GO loading. The dielectric loss (tan delta) has increased from 1.56 (50 KHz, 140 degrees C) for PSSA/PVA (50/50) blend to 2.64 (50 KHz, 140 degrees C) for PSSA/PVA/GO composites with 3 wt % GO loading. These findings provide a new insight to fabricate flexible, high-lc dielectric composite as a promising material for energy storage applications. (C) 2016 Elsevier B.V. All rights reserved.