In order to study the friction and wear mechanism of PEEK and nano-SiO2 filled PTFE composites under dry friction condition, the friction and wear tests were carried out on LSR-2M reciprocating friction and wear tester. The samples were prepared by the blending-cold pressing-sintering process. Scanning electron microscope (SEM) and non-contact 3D profiler were used to characterize the microscopic morphology of the transfer film and wear track on the counterpart surface, and the X-ray energy spectrum analysis (EDS) was used to characterize the elements distribution on the counterpart surface. The results show that the friction and wear properties of PTFE composites can be improved with PEEK and nano-SiO2 filled separately. Among them, the volume wear rate of 20% PEEK-PTFE composite is only 2.6×10-6mm3/(Nm), and the mean friction coefficient of 15% PEEK-PTFE composite is 0.18. The antifriction effect of the composite that filled with nano-SiO2 is not as good as that of PEEK, but when they are filled together can synergistically improve the tribological properties of PTFE composites. After 5 hours wear, the volume wear rate of 15%PEEK-PTFE composites reduced to 2.7×10-6mm3/(Nm), and 3% nano-SiO2-15%PEEK-PTFE composites reduced to 4.3×10-6mm3/(Nm). When the counterpart surface roughness increased, the volume wear rate of the two composites increased, but the mean friction coefficient decreased.