This paper reports the synthesis of the VO x –WO y /TiO 2 -palygorskite composite catalysts via mixed impregnation method. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The fibers of palygorskite retained the original morphology upon calcination. The VO x –WO y /TiO 2 (VWT) particles were attached on the surface of the palygorskite. The mass ratio of VWT to palygorskite showed an obvious effect on the coating condition of VWT onto the palygorskite, which also affected the catalytic performance. The composites had the highest catalytic activity of 90% to orto-dichlorobenzene (o-DCB) at the mass ratio of 2:1.