In this paper, the tribological properties of polytetrafluoroethylene (PTFE) composites filled with Nano-ZrO2 and polyetheretherketone (PEEK) particles were tested for sliding friction against a counterpart metal (ASTM 1045 steel) using a linear reciprocating friction and wear experimental machine. Data on tribological performance and optical images of the transfer film were obtained at various friction stages for the material. MATLAB software was employed to develop quantitative analysis procedures for the morphological characteristics of the transfer film. The program enables image enhancement and morphological processing of transfer film images, then identifies, extracts, and quantifies the geometric and textural properties of the transfer film as a foundation for analyzing the variation of the characteristics and their relationship to the tribological properties of the material. The results demonstrated that the geometric, morphological, and textural characteristics of the transfer film were dynamically developing during the friction process, with noticeable differences between various friction stages and a significant impact on the tribological properties of the material. Quantitative analysis revealed a good correlation between the trends of some morphological and textural characteristics (the coverage, area, diameter, roundness, consistency, and texture entropy) of the transfer film and the wear resistance of the PTFE composite. Therefore, these morphological and textural characteristics can thus be used to quantify the transfer film quality and utilized as an indirect indicator of the tribological properties of the material.