A hybrid of attapulgite (ATP) nanofibers loaded with titanium dioxide (TiO2) nanoparticles was prepared by a steam-based method, and different contents were used for the reinforcement of ultra-high molecular weight polyethylene (UHMWPE) matrix. The results show that the thermal conductivity of the composites increased with increasing ATP-TiO2 content, and its optimal wear resistance was obtained at 5 wt% filler content, reducing of friction coefficient and wear loss by up to 33.3% and 49.4%, respectively. With the homogenous distribution of an appropriate amount of the ATP-TiO2 hybrid in the matrix, the network structure formed by the fillers was conducive to heat conduction and thus improved the thermal stability of the composites. Furthermore, the fillers promoted the formation of transfer film that prevented severe damage caused by metallic counterpart. This study of the microstructure and transfer behavior of ATP-TiO2 hybrid reinforced UHMWPE paves the way for expanding its application to fretting wear conditions.