In this paper, the friction and wear behaviors of filled PTFE/steel couples are studied. The stationary specimen was made of filled PTFE. The rotating specimen, made of steels, underwent various treatments. The experimental results showed that the frictional coefficient and wear rate were low when the surface of the steel specimen contained nitrogen. The structure of the transfer film was examined by X-ray photoelectron spectroscopy (XPS). The transfer film containing nitrogen on the steel surface was thick. The authors consider that the hypothesis of the adhesion of the n-p-n structure may explain the characteristics of the different sliding couples in this paper and might be an important way to improve the friction and wear properties of the filled PTFE/metal sliding couples.