Using argon as the work gas, the effects and mechanisms of poly(tetrafluoroethylene) (PTFE) film surface modification were investigated in a low pressure plasma reactor. Results show that higher hydrophilicity with little degradation, in terms of the scanning electron microscopy (SEM), was obtained after treatment, especially when the sample was placed in the post-discharge area. More polar functional groups and higher surface free energy, especially the polar component, formed on the PTFE surface were responsible for the modification. For the relatively high purity radicals and rare discharge particles in the post-discharge area, the etching was restrained and the introducing reactions were enhanced, and thus, a better modification occurred there.