The formation of plasma-polymerized materials made from organic molecules is a technologically attractive way to obtain films with unique properties for life science applications. Surface properties like bio-compatibility, wettability, etc., can be adjusted by tailoring the chemical functionalization. It is well known that after deposition these films undergo post-plasma reactions, especially when they are exposed to ambient atmosphere. Most often, in applications these films are not used immediately after their deposition – they are usually stored for a certain time. Therefore there is a need for a development of analytical procedures enabling studies of ageing phenomena of plasma chemically deposited films. With the help of these studies a better understanding of basic post-plasma reaction phenomena as well as relevant empiric information for practical applications can be obtained. However, a detailed chemical characterization of plasma chemically deposited films is a great challenge for the analysts because of the co-existence of a number of different chemical species. We investigated r.f. plasma-polymerized organic films by using photoelectron spectroscopy for chemical analysis (ESCA), spectroscopy of the near edge X-ray absorption fine structures (NEXAFS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). Ethylene, styrene, allyl alcohol and allyl amine were used as monomers. A dedicated plasma preparation chamber was designed and added to the main analysis chamber of the respective spectrometer. This approach offers the possibility to study plasma-polymerized films in situ and, subsequently, the influence of post-plasma reactions. The important effect of air exposure of the film, in terms of plasma technology denominated as “ageing”, can be studied subsequentially step by step by this unique approach.