Synopsis Complexes of glycosaminoglycans and certain cationic polymers have been identified which provide utility in skin and hair care applications. The combination of biologically engineered hyaluronic acid and the cationic cellulose polymer, polyquaternium-10, results in a unique, stable, multifunctional, association complex with enhanced polymer functionality. Complexation of the anionic and cationic polysaccharide polymers renders hyaluronic acid substantive to keratin, as evidenced by zeta potential changes of the surface charge of hair via electrokinetic streaming potential measurements. Radiolabelling techniques show as much as a ten-fold increase in bound hyaluronic acid on hair after water rinsing. The resulting 'enhanced'substantivity of hyaluronic acid, as part of the complex, thus extends the time hyaluronic acid remains in contact with keratinous surfaces, prolonging its humectant, moisturizing and skin-smoothening effects.