Novel protonated palygorskite/chitosan resin microspheres (p-PCRM) were prepared and applied as adsorbents for the removal of tannic acid (TA) from aqueous solution. The effects of palygorskite (PAL) content, the initial pH value of the TA solution, and contact time and temperature on adsorption capacity of the microspheres were investigated. The adsorption process was found to be pH dependant with an optimum activity at pH 8.0. In comparison with protonated chitosan microspheres (224 mg g(-1)), the p-PCRM with 20 wt % PAL content exhibited higher adsorption capacity (455 mg g(-1)) for TA at the same adsorption conditions. This may be attributed to the hydrogen bonding between adsorbents and adsorbates, and the porous structure formed by the introduction of PAL, which were confirmed by Fourier transform infrared and the pore parameters analysis. The study of adsorption kinetics and isotherms showed that the sorption processes were better fitted by pseudo-second-order equation and the Langmuir equation, respectively. Furthermore, the desorption study implied that the p-PCRM were recyclable when 0.1M HCl was used as eluents. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013