The aim of this paper is to enhance the knowledge on the behaviour and thermodynamic properties of natural and synthetic biopolymers in aqueous solutions. The acid-base properties of Carrageenan (Car), Xanthan gum (XG), Hydroxyethyl cellulose (HEC), Carboxymethyl cellulose (CMC), Acusol 445™ (Sol), Monopropylene glycol (MPG) and Polyethylene glycol (PEG) have been studied by potentiometric technique in NaNO3(aq), at I = 0.15 mol dm−3 and T = 298.15 K. In some cases, the protonation constants have been determined at different ionic strengths, and the dependence on ionic strength has been modelled by a Debye-Hückel type equation. The binding ability of the different polymers has been investigated towards Ca2+, Zn2+ and Sn2+ and, different speciation models have been obtained. For Acusol 445™, the weak interactions with Na+ and K+ have been determined. The effect on the complexing ability of a secondary inorganic ligand, the fluoride, has been evaluated on Carboxymethyl cellulose and Acusol systems; the formation of ternary mixed complexes with a significant increasing stability with respect the binary species has been obtained.The sequestering ability of the polymers towards the metal cations has been evaluated by means the empirical parameter pL0.5.