Primary amine-based plasma polymer films (PPF) attract an increasing interest due to their potential applications as platforms to support cell growth and biomacromolecule immobilization. It has been demonstrated that the biological response of these films is correlated to their primary amine content (%NH2). Control and optimization of the process are thus very important requirements. However, despite the abundant literature related to this attractive technology, plasma polymerization remains very complex so that strong efforts are still needed to understand the relationship between the plasma chemistry and the PPF characteristics. The main part of this work describes the pulsed plasma polymerization of two isomeric precursors, namely allylamine and cyclopropylamine, with the aim to study the influence of the precursor on the plasma and the PPF physico-chemistries. The systems have been compared in similar conditions of mean power injected in the discharge (Pmean). Both experimental and theoretical approaches have been used to shed light on the process. Taking into account the electron energy in the plasma, differences between allylamine and cyclopropylamine plasma chemistries have been rationalized with the help of Density Functional Theory calculations. It is demonstrated that %NH2 can be increased by an appropriate choice of the precursor and the experimental conditions. Indeed, the use of cyclopropylamine can yield to PPF with a larger %NH2 compared to allylamine due to a preferential opening of the ring structure in the plasma. A method is also proposed to discriminate the PPF according to their cross-linking density (÷). While it appears to be independent of the chemical structure of the precursor, ÷ is observed to significantly vary with Pmean. The PPF have further been investigated with the aim to better understand the phenomena taking place when immersed in liquid medium, an essential step for biological applications. The results show that the decrease in the PPF thickness (Äd), conventionally observed upon immersion, directly depends on Pmean; the higher Pmean, the lower Äd. For the first time to our knowledge, the present work allows to unambiguously attribute this phenomenon to an increase of ÷ with Pmean. Furthermore, thanks to the analysis of the resulting solutions, the data give a new insight into the PPF behavior in liquid medium, suggesting that Äd is mostly related to a reorganization of the PPF network and not to material dissolution as usually claimed. Finally, some preliminary experiments indicate that the PPF can be used to support muscle cell culture; the performances of the PPF-coated materials reveal to be at least similar to those of the standard surfaces.