The partitioning of three polysaccharides, Dextran sulfate (DxS), A-Carrageenan (CAR), and Dextran (Dx), and its dependence on polymer charge density and ionic strength have been investigated in the segregative mixture of poly(sodium styrene sulfonate) (NaPSS) and sodium polyacrylate-acrylamide copolymers, NaP(AA/AM), of variable charge density, in aqueous Solutions. It is shown that the Solubility of all the three may be zero or finite in one or both phases, but the preferred phase is determined by the charge density on the copolymer. When charge densities are equal on the phase forming polymers, the saccharides CAR and Dx favor the phase rich in PSS, but they have greater affinity for the polymer of lower charge density when the charge densities on phase polymers are unequal. The partitioning behavior of DxS is the opposite of the other two polysachharides with respect to which phase it has the greatest affinity for. The values of the partitioning coefficients show that the system may be potentially useful for the purification of polysaccharides and other macromolecules, if appropriate conditions are selected. (c) 2006 Wiley Periodicals, Inc.