The chemical inertness, thermal stability, and low dielectric constant characteristics of polytetrafluoroethylene make this polymer very attractive for advanced technology applications. Current production technologies are not adequate for the deposition of often desired, thin-layer Teflon coatings. In this article the synthesis and characterization of Teflon-like macromolecular structures from do decafluorocyclohexane and octadecafluorodecaline vapors under RF-cold-plasma conditions is discussed. It was demonstrated, based on high-resolution ESCA, ATR-FTIR, and LD-FT-ICR-MS investigations, that the deposited Teflon-like layers are built of CF, CF,, CF,, and ex situ origin C-O groups with an over 60% fluorine content, and that they have a branched and/or crosslinked nature. These structures have a relatively high thermal stability (340 degrees C) and are characterized by a low dielectric constant (2.1). Plasma enhanced coatings of Teflon-like layers can be performed at room temperatures at large substrate areas.