This study employed a high-speed rotating crushing process to modify pyrolyzed carbon black (CBp) using self-lubricating and low-friction polytetrafluoroethylene (PTFE). The effects of PTFE content on the dispersion, mechanical properties, wear resistance, and thermal stability of modified PTFE-CBp/natural rubber (NR) composites were investigated. The rotating crushing process from the high-speed grinder altered the physical structure of PTFE, forming tiny fibrous structures that interspersed among the CBp particles. This arrangement encouraged the alignment of CBp particles in specific directions and improved the surface activity of CBp, enhancing the dispersion of CBp within the NR matrix and consequently improving wear resistance. The experimental results indicated that as the amount of PTFE fibers increased, the hardness, wear resistance, and thermal stability of the PTFE-CBp/NR composite significantly improved. Compared to untreated CBp/NR composites, the hardness, modulus at 300%, and wear resistance of the 3 phr PTFE-CBp/NR composites increased by 20%, 24%, 21%, respectively, achieving the preparation of highly wear-resistant CBp/NR composites.