In the present study, we report the fabrication and characterizations of flexible dielectric nanocomposites consisting of water soluble polypyrrole (WPPy)/polyvinyl alcohol (PVA)/graphene oxide (GO) at different GO loadings (0.5–3 wt%). The WPPy/PVA/GO nanocomposites were characterized using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, UV-vis spectroscopy (UV), X-ray diffraction (XRD), thermogravimetric analysis (TGA), polarized optical microscopy (POM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). FTIR studies indicate the strong chemical interaction between GO and polymer systems. SEM results confirm that GO was homogeneously dispersed within the polymer matrix. The nanocomposites exhibit significant enhancement in the dielectric constant with low dielectric loss values as a function of GO loading which resulted from the fine dispersion of GO in the polymer matrix. The dielectric constant increases from (ε = 27.93, 50 Hz, 150 °C) for WPPy/PVA (50/50) blend to (ε = 155.18, 50 Hz, 150 °C) for nanocomposites with 3 wt% GO loading and the dielectric loss increases from (tan δ = 2.01, 50 Hz, 150 °C) for WPPy/PVA (50/50) blend to (tan δ = 4.71, 50 Hz, 150 °C) for nanocomposites with 3 wt% GO loading. Thus, these high-κ WPPy/PVA/GO nanocomposites are potential flexible high-performance dielectric materials for electronic devices such as high-frequency capacitors or embedded capacitors.