An air diffuse coplanar surface barrier discharge is used to activate the surface of polytetrafluoroethylene (PTFE) samples, which are subsequently coated with polyvinylpyrrolidone (PVP) and tannic acid (TAN) single, bi-and multilayers, respectively, using the dipcoating method. The surfaces are characterized by X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflection -Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Atomic Force Microscopy (AFM). The XPS measurements show that with plasma treatment the F/C atomic ratio in the PTFE surface decreases, due to the diminution of the concentration of CF 2 moieties, and also oxygen incorporation through formation of new C-O, C=O and O=C-O bonds can be observed. In the case of coated samples, the new bonds indicated by XPS show the bonding between the organic layer and the surface, and thus the stability of layers, while the gradual decrease of the concentration of F atoms with the number of deposited layers proves the creation of PVP/TAN bi-and multi-layers. According to the ATR-FTIR spectra, in the case of PVP/TAN multilayer hydrogen bonding develops between the PVP and TAN, which assures the stability of the multilayer. The AFM lateral friction measurements show that the macromolecular layers homogeneously coat the plasma treated PTFE surface.