The binding of three different amphiphiles (with different hydrophobic characters) to oppositely charged polyelectrolytes (κ‐carrageenan, dextran sulphate, alginate, and hyaluronan) is investigated. It is shown that the degree of binding is related not only to the hydrophobicity of the amphiphile and to the charge density of the polyelectrolyte, but also to the flexibility of the polyion. Furthermore, the cooperativity in the binding of amphiphile to polyelectrolyte was observed in all cases except for hyaluronan, which showed a very weak adsorption isotherm. The effect of polyelectrolyte concentration on the adsorption isotherm was also investigated for dextran sulphate and alginate. The effect of concentration was found to be weak. © 1997 John Wiley & Sons, Inc. Biopoly 41: 765–772, 1997