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Plasma polymer thin films are of great interest in surface engineering in a wide range of applications.Herein, by using soft atmospheric plasma deposition parameters and by adapting these conditions to the used perfluorodecyl and dodecyl acrylates precursors, it is possible to get a high retention of monoemer functionalities and a polymerization close to conventional methods.The deposition of organized plasma polymer molecular films Atmospheric Pressure Dielectric Barrier (APDBD) discharge is described.Molecular investigation revealed the presence of polymeric moieties and the mechanism of plasma polymnerization has been mainly based on the polymerization by activation of the ethylenic groups.X-ray diffraction analyses have shown the presence of a smectic lamellar where the polyacrylate backbone was the amorphous phase and fluorinated and alkyl side chains were the hexagonal crystalline section.Wetting and mechanical properties have been evaluated and finally evidenced different behaviours according to the temperatures.By this method, multifunctionai plasma polymers thin coatings have been finally achieved with an unusual degree of control.