Interactions between the mixtures of fluorine surfactants (FS) of different chemical character (anionic - Capstone FS-64, cationic - S-106A and non-ionic - Capstone FS-30) and polysaccharides (anionic - carboxymethyl cellulose (CMC), cationic starch (CS) and non-ionic - hydroxyethyl cellulose (HEC)) have been investigated by surface tension, viscosity and nuclear magnetic resonance (NMR). The factors governing the formation of polysaccharide surfactant complexes (PSC) were discussed in terms of the electrostatic and hydrophobic interactions. The surface tension and viscosity measurements allow to find out in which systems the interactions occur and also when they start and end. NMR was studied not only to analyse the chemical structures of the fluorine surfactants but also to determine the characteristics of PSC. (C) 2019 Elsevier B.V. All rights reserved.