There is an increasing demand for air-dry performance of fluorocarbon finished materials. Thus, surface modifications of wool fabrics were evaluated. Untreated, gaseous fluorinated, Chlorine/Hercosett processed 100 % wool fabrics were treated with different fluorochemicals and their liquid repellency after washing, and dry cleaning were evaluated. The results indicated that Chlorine-Hercosett treated samples, wool with a positive charge, after few washing cycles, showed better air dry performance with higher level of repellent properties. In addition, the comparison of the wool surface modifications treatment with different applied fluorochemicals, with different commercial formulations, illustrated that the fluorocarbon chain re-orientation and fastness properties are more affected by the nature of the wool surface while the used fluorocarbons showed more or less similar behaviours. In general, the fluorination increases fabric stiffness with lower fabric formability. The surface interface was effectively probed by X-ray Photoelectron Spectroscopy, XPS, which enabled the characterisation of the loss of surface lipids, the nature of the fibre oxidation and the deposition of fluoropolymers.