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Surface modification of wool, polyamide 6 and cotton fabrics was investigated with an Ar–CF4 post-discharge plasma. The radical F, as determined by optical emission spectroscopy, is considered to be the main active species acting on the fabrics and producing different effects as a function of the textile substrate. Fluorination of the surface is achieved on the three materials studied, but only wool and polyamide 6 fluorinated surfaces become hydrophobic at long treatment times, and show antibacterial properties. The treatment conditions used are mild enough so as not to alter surface topography, as confirmed by scanning electron and atomic force microscopy.