Aqueous solutions containing poly(vinylpyrrolidone) (PVP) and sodium caprylate (SCAP) or tetraethylammonium perfluorooctanesulfonate have been investigated as a function of the surfactant content, the added polymer, temperature and ionic strength. According to experimental evidence, significant interactions have been observed in both systems, with the occurrence of both critical association and micelle formation thresholds. Volumetric, viscometric, ionic conductivity and surface tension methods have been used to quantify the interactions between surfactants and the polymer in ternary systems containing PVP and SCAP or the polymer and the fluorinated surfactant. In both cases, the width of the interaction region is proportional to the PVP content in the mixture. Temperature and ionic strength have a relevant effect on the width of the interaction region, which decreases on increasing the temperature. Binding onto PVP and micelle formation were analyzed in terms of a mass-action model. In this way, the observed behavior was rationalized and information on the thermodynamics of such mixtures was given.