Teflon-like thin layers were deposited on various substrate surfaces from perfluoro-1-butanesulfonyl fluoride/methane radio frequency pulsed plasma environments. The deposited films were characterized using attenuated total reflectance Fourier transform infrared spectroscopy, electron spectroscopy for chemical analysis, differential thermal analysis/thermogravimetric analysis (DTA/TG), and atomic force microscopy techniques. It has been demonstrated that the presence of methane is crucial for the deposition of fluorinated structures due to the simultaneously developed and fluorine atoms controlled competitive etching and deposition processes. It has been shown that plasma films with the highest fluorine concentrations can be generated under low duty cycle and high methane partial pressure conditions. DTA/TG data indicate that the Teflon-like layers have a fairly high thermal stability.