This work presents the development of high-performance thermoplastic polyurethane (TPU) nanocomposites reinforced with low contents of multilayer graphene (mG), aiming to improve their tribological behavior. Using twin-screw extrusion followed by hot pressing, nanocomposites containing 0.1, 0.25, 0.5, 1, and 2% mG weight were fabricated and systematically evaluated. Nanocomposites with only 0.1–0.25 wt% mG achieved a 36% reduction in friction coefficient and 87.5% reduction in wear volume compared to neat TPU. Results are rarely reported at such low filler loadings. Scanning electron microscopy (SEM) analysis revealed uniform dispersion at these optimal concentrations, while higher mG contents led to agglomeration and performance loss. Rheological studies indicated improved flow behavior, and dynamic-mechanical analysis confirmed increased energy dissipation and thermal response. These results suggest that the concentrations of 0.1% and 0.25% of multilayer graphene used in the study are promising for improving the performance of TPU nanocomposites in applications requiring high wear resistance for advanced applications in automotive, biomedical, and high-load engineering components, where durability and low friction are essential.