Polyetheretherketone (PEEK) is widely used across various industries because of its high thermal stability, chemical resistance, and superior mechanical properties. This paper introduces an optimized method for dispersing functionalized graphene to improve the frictional and electrical resistance properties of PEEK. The influence of graphene, recognized as an effective additive, on the melt behavior, thermal stability, and tribological and electrical properties of PEEK–graphene nanocomposites was assessed for different filler contents. Results show that graphene acts as a nucleating agent, enhancing crystallinity in PEEK–graphene nanocomposites. A nanocomposite containing 1.0 wt.% graphene exhibited optimal frictional performance and surface resistance. Additionally, the study reveals that the integration of hybrid additives with varied shapes fosters the formation of three-dimensional particle networks more effectively than graphene additives alone.