Cosmetic and medical applications of technical textiles are a research expanding field. One of the added values of these new materials would be that they are suitable to contain and release active ingredients in a controlled manner. The influence of the initial state of the surface of polyamide 6.6 (PA66) fibers on the wetting properties of the fibers as well as on the incorporation of caffeine on the fibers and on its release kinetics from the fibers has been investigated. Comparison between industrially-finished PA66 fabrics and laboratory washed fabrics has been done to carry out this study. Furthermore, surface modification of the PA66 fibers by low temperature plasma has been studied regarding the modification of the physical, chemical and topographical properties of the textile fibers. Corona plasma treatment has been investigated to achieve surface modification in the first nanometers of polymer fibers surface in order to modulate the incorporation and the release of caffeine. It has been demonstrated that both initial state of the PA66 surface and prior plasma treatment of the PA66 fibers before the active principle incorporation condition caffeine release kinetics from the textile fibers. The final release percentage increases linearly with the C–O and C O functional groups incorporated by plasma on the surface. It has also been established that the release amounts of caffeine achieved after 8 h from the PA66 fabric are in the same order of magnitude than topical doses of commercial gel-based formulations