The materials tribology community has identified that the transfer film attached to the surface of the counterpart metal during the friction process is not only closely related to the filler modification material but also a key factor affecting the tribological properties of polymer composites; however, there is a lack of feasible methods to quantify the characteristics of the transfer film. In this study, Nano-ZrO2 and polyetheretherketone (PEEK) were filled into a PTFE matrix in order to enhance the wear resistance of polytetrafluoroethylene (PTFE). The tribological properties of the modified PTFE composites were tested using a linear reciprocating friction and wear tester, and the entire friction experiment was designed in seven separate stages. Morphological features were extracted and analyzed from photographs of the transfer film acquired by optical microscopy at each friction stage using an image processing program. The thickness and roughness of the transfer film sections were measured using a non-contact profilometer. Abrasive debris were collected, and their morphological features were observed with an electron microscope. The results showed that the synergistic addition of soft PEEK and hard Nano-ZrO2 particles effectively inhibited interlayer slippage between PTFE molecular chains, dramatically reducing the size and yield of abrasive debris, and facilitated the improvement of the thickness and firmness of the transfer film, which significantly enhanced the wear resistance of the PTFE composites (the lowest volumetric wear rate for Nano-ZrO2/PEEK/PTFE was only 1.76 × 10-4 mm3/Nm). Quantitative analyses of the morphological characteristics of the transfer films revealed that the coverage and roundness of the transfer films gradually increase with the friction stroke, while the aspect ratio and texture entropy subsequently decrease gradually. The coverage, area, mean, third-order moments, and consistency of the transfer film strongly correlated with the volumetric wear rate (correlation coefficient |r| > 0.9).