Background: The addition of nanofillers to polymers for enhanced performance is delivering more interesting applications for aerospace, aeronautic industries, and other numerous nanotechnical applications. Objective: The aim was, therefore, to examine the role of graphene nanopowder on the thermal stability and conductivity of the poly(vinyl alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) polymer nanocomposites. Methods: In this work, graphene nanofillers were incorporated into the PVA/PVP polymer blended by solution mixing for the preparation of nanocomposite films. Results: Results showed that increasing graphene ratio improved thermal conductivity up to 330%, moreover enhancing hardness shore A up to 16.3% compared to pure PVA/PVP blend polymer. TGA analysis confirmed that the PVA/PVP and graphene network showed good thermal stability. Conclusion: From the present findings, it is proved that PVA/PVP blends have profound effects on thermal stability that cannot be attained by using individual counterparts. The property of the nanocomposite depends on the host blend, morphology, and interfacial characteristics.