The attapulgite nanofibers (ATP) were grafted on the surface of carbon fibers (CF) by polyetherimide (PEI) with long chain to reinforce the thermal, mechanical properties, and fretting wear resistance of ultra-high molecular weight polyethylene. The results showed that the surface roughness of CF modified by ATP nanofibers were highly increased. Meanwhile, the thermal, mechanical, and tribological properties of the ATP-PEI-CF/UPE composite were significantly improved, especially the enhancement in heat distortion temperature, compressive modulus, and wear resistance. The improvement mechanisms of the corresponding properties were mainly attributed to the increase of mechanical interlocking of the matrix and the hybrid fillers, which could not only transfer the load and heat applied to the matrix to the fibers, but also impede the friction damage of the matrix during fretting wear process.