Abstract Binding of cations to chondroitin sulfate A and C, Chondroitin, and D-glucuronate was investigated in neutral and acidic aqueous media using H +, Cu 2+, and Na + ion-specific electrodes, viscometry, electron spin resonance (esr), and ligand-field spectroscopy. Site binding to the carboxylate group and only electrostatic interaction with the sulfate group could describe the results well. The nitrogen atom of the N-acetyl group appeared not to be involved in bonding of cations to chondroitin(sulfate) systems. The interaction of the divalent metal ions follows the Irving-Williams series. The value of the electrostatic potential at the carboxylate group of chondroitin(sulfate), as experienced by a cation, was determined in dependence of cation bonding. It proved to be difficult to establish the composition of a complex of a metal ion with a polyion by means of a molar ratio curve.