Nano-ZrO2 and PEEK particles were synergistically filled in unfilled PTFE to improve the wear resistance and maintain a relatively low friction coefficient, and the materials were studied using a reciprocating sliding friction and wear tester. In the friction tests, the evolution of various tribological characteristics in both the contact interfaces and debris was observed, and the wear mechanism of the PTFE composites was investigated. The results showed that the wear rate of the PTFE composites synergistically filled with nano-ZrO2 and PEEK was lower and its friction coefficient was slightly higher than that of the unfilled PTFE; the uniformity and continuity of the transfer film generated by the composite with nano-ZrO2 and PEEK were the best, and the particle size of the debris was minimal in comparison to that in other sample systems.