The retention of chemical structure and functional groups during plasma polymerization was investigated. Low wattage and pulsing of the radio-frequency low-pressure glow discharge proved to be successful in the formation of well-defined polymer structures. Furthermore, unsaturated plasma deposited polymers were simultaneously doped with metals. The combined process was realized in one and the same reactor by a quick moving of the sample through the plasma deposition and the metal evaporation zones. The two zones were geometrically divided from each other. The polymer structure and the chemical interactions between the plasma polymer matrix and the ambient air were analyzed by XPS, IR and NEXAFS. Plasma polymer layers with a high content of functional groups, generally well-suited to form defined chemical interactions with metal toplayers, were deposited from allylalcohol and acrylonitrile. The dependency of the intactness of OH and CN functional groups in plasma polymer layers on the plasma deposition parameters was studied. To avoid the well-known ageing and auto-oxidation of plasma polymers the pulsed plasma deposition technique was successfully employed. Moreover, thermal and chemical quenchings of the nonreacted trapped carbon radicals were performed. For chemical quenching the sample was exposed to NO.