Novel chitosan gel beads were synthesized by a coupled ionic and chemical co-crosslinking mechanism. Tripolyphosphate (TPP) and a naturally occurring crosslinking reagent, genipin, which has been used in herbal medicine, were employed, respectively, as an ionic and a chemical crosslinkers to prepare the chitosan-based networks of gel beads. The competitive crosslinking of chitosan with ionic crosslinker (TPP) and chemical crosslinker (genipin) was characterized by FTIR, UV and EDAX spectroscopy (X-ray energy dispersion) spectroscopy. The variation of characteristic peak of genipin observed from UV spectroscopy and the characteristic peak of tripolyphosphate in crosslinked chitosan-based networks observed from FTIR spectroscopy suggests that the co-crosslinking mechanism is dependent on the pH of TPP/genipin co-crosslinker. The energy profiles of carbon and phosphorus estimated from confirms that chemical crosslinking dominates the co-crosslinking reaction at higher pH condition (pH 7.0 and 9.0) and ionic crosslinking dominates the co-crosslinking reaction at lower pH condition (pH 1.0, 3.0 and 5.0). The pH-dependent ionic/chemical co-crosslinking mechanism shows an obvious effect on the swelling property and enzymatic degradation behavior of prepared chitosan networks. These results reveal that the ionic/chemical co-crosslinked chitosan networks may be suitable for biomedical applications. (C) 2003 Published by Elsevier Ltd.