AgBr/palygorskite composite was prepared by an in situ electrostatic adsorption-deposition-precipitation method and characterized by field emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), UV-Vis diffuse reflection, and BET surface measurements techniques. The layer negative charge and larger specific surface area of palygorskite, along with the poor cation-exchange ability of tetra-n-butyl ammonium cation (N(CH2CH2CH2CH3)(4)(+)) due to its larger ion radius, could mainly account for high dispersity of AgBr on the surface of fibrous palygorskite. The rate of Rh B decolorization and CO2 reduction with H-2 as a proton donor and reductant over AgBr/palygorskite was about three and two times faster than that of the corresponding bare AgBr, respectively. The strategy reported in this work can be easily extended to synthesize other palygorskite-based heterostructure catalysts. (C) 2012 Elsevier Inc. All rights reserved.