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In the present study, graphene oxide (GO)-reinforced poly (4-styrenesulfonic acid) (PSSA)/polyvinyl alcohol (PVA) blend composite films were prepared using colloidal blending technique at various concentrations of GO (0–3[Formula: see text]wt.%). The morphological investigations of the prepared composites were carried out using polarized optical microscopy and scanning electron microscopy. The electrical properties of composites were evaluated using an impedance analyzer in the frequency range 50[Formula: see text]Hz to 20[Formula: see text]MHz and temperature in the range 40–150[Formula: see text]C. Morphological studies infer that GO was homogeneously dispersed in the PSSA/PVA blend matrix. Investigations of electrical property indicate that the incorporation of GO into PSSA/PVA blend matrix resulted in the enhancement of the impedance ([Formula: see text] and the quality factor ([Formula: see text]-factor) values. A maximum impedance of about 4.32[Formula: see text][Formula: see text][Formula: see text]10[Formula: see text] was observed at 50[Formula: see text]Hz and 90[Formula: see text]C for PSSA/PVA/GO composites with 3[Formula: see text]wt.% GO loading. The [Formula: see text]-factor also increased from 8.37 for PSSA/PVA blend to 59.8 for PSSA/PVA/GO composites with 3[Formula: see text]wt.% GO loading. These results indicate that PSSA/PVA/GO composites can be used for high-[Formula: see text] capacitor applications.