In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et 4 NI and NaCl (for fulvic acid 0.1<I /mol L −1 <0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5<S<45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na + , K + , Mg 2+ , Ca 2+ ) and anions (Cl − , SO 4 2− ) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments.