Organosilicon plasma polymers were deposited on polyvinyl alcohol and polyamide 6 electrospun nanofibers from hexamethyldisiloxane/Ar mixtures in low pressure (LP) radio frequency (RF) discharges with capacitive coupling and by cold RF plasma multi‐jets working at atmospheric pressure (AP). The chemistry of the films deposited at LP was significantly varied by changing the RF power and process pressure as studied by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Both the gas phase and surface processes contributed to the observed differences in the film properties. Significant variations in the nano/microstructure of the plasma polymers prepared by plasma processes at two different pressures were revealed by Atomic force microscopy and Scanning electron microscopy analysis. Modifications of the fibrous materials were investigated with respect to the wettability and structural properties. The values of the water contact angle were strongly influenced by both, the chemical composition of the deposited layers and the overall surface structure.