In this work, we describe an effective route to synthesize Ag-AgCl/WO3 hollow sphere with flower-like structure, which displayed excellent visible light response photocatalytic activity and recycling ability for the degradation of 4-chlorophenol. Its high photocatalytic activity can be attributed to the surface plasmon resonance effect of Ag nanoparticles, which were highly dispersed on the surface of Ag-AgCl/WO3. N-2 adsorption and desorption isotherm spectra, X-ray diffraction, X-ray photoelectron spectroscopy. and electron microscopy were used to determine the correlation between the micro-structure and the catalytic properties of the as-prepared photocatalysts. (C) 2012 Elsevier B.V. All rights reserved.