The surface modifications of reinforcing components have significant influence on the tribological performance of resin-based friction composites. In this work, 3-aminopropyltriethoxysilane coupling agent (KH550) and octadecyltrichlorosilane (OTS) were used to modify nanosized potassium titanate whiskers (PTW). Subsequently, the modified potassium titanate whiskers were used as reinforcing components in phenolic resin-based friction composites. The tribological behavior and wear mechanism of the composites were studied. The results show that the surface free energy of 5% OTS-modified potassium titanate whiskers is the closest to that of the resin matrix, which is 26.4 mJ/m2. Moreover, the OTS-modified PTW-reinforced composites possess a more stable friction coefficient and a lower wear rate at high temperature. The OTS-modified PTW-reinforced composite (O-C) has a 19% lower total wear rate than the unmodified PTW-reinforced composite (P-C). That is mainly because the modified potassium titanate whisker is more evenly distributed in the resin matrix and tightly bonded to the resin. Results demonstrate that OTS-modified PTW-reinforced composites displayed preferable tribological performance. This article provides a new method for PTW modifications in improving the tribological performance of the resin-based friction composites.