A new biocomposite was prepared by incorporating inorganic ion exchanger namely zirconium(IV) tungstophosphate (ZrWP) into the chitosan biopolymeric matrix. The sorption behaviour of fluoride from aqueous solutions by this ZrWP/chitosan (ZrWPCs) composite has been investigated by batch technique. The fluoride sorption was studied as a function of contact time, pH, initial fluoride concentration, competing co-ions and temperature. The defluoridation capacity (DC) of the adsorbent was found to be 2025 mgF(-) kg(-1). The composite was characterized using FTIR and SEM with EDAX analysis. The equilibrium sorption data were fitted to Freundlich and Langmuir isotherms. The kinetics of sorption was found to follow pseudo-second-order and intraparticle diffusion models. The values of thermodynamic parameters indicate the nature of sorption is spontaneous and endothermic. The biocomposite was successfully used for the removal of fluoride from the field water taken in a nearby fluoride endemic village. (C) 2009 Elsevier B.V. All rights reserved.