Proton NMR investigations on lithium heptadecafluorononanoate, LiPFN, in poly(vinylpyrrolidone), PVP, aqueous solutions have been carried out. NMR spectra reveal that the amphiphile, in its micellar form, links to the polymer chains by hydrophobic interactions with the pyrrolidone functional group of the polymer, causing a significant change in the PVP structure. Surface tension, viscosity, and volume measurements on LiPFN-PVP-water systems support the NMR evidence.