The possibility of generating tailored surface characteristics (adhesion, biocompatibility, wettability, etc.) from plasma modified surfaces by derivatization and grafting reactions, opens up new possibilities for the creation of advanced materials. Implantation of reactive amine (primary amine) functionalities onto synthetic polymeric surfaces under cold plasma conditions- one of the potential approaches to surface functionalization has been the subject of numerous investigations of recent years. It has been shown that ammonia plasmas do not implant primary amine groups efficiently and consequently, a large number of amine-group containing compounds were tested as alternatives. However, the low volatilities of many of potential aminating agents limit considerably their plasma processing. In this contribution a novel approach of surface amination of PP samples from melamine and urea precoated surfaces is presented. ESCA, ATR-FTIR and ex-situ post plasma grafting reaction data indicate that simultaneous plasma induced evaporation, fragmentation and primary amine implantation processes can be successfully developed. The surface primary-amine concentrations were evaluated by chemical derivatization technique, and the influence of plasma treatment time on the amine group concentrations was investigated.