Hierarchical porous AgCl@Ag hollow architectures (HAS) were successfully synthesized by a facile, inexpensive and scalable approach through template-engaged acidic etching of uniform Ag2CO3 architectures at room temperature. The critical surface chlorination and pore creation were realized by using NH4Cl as a reactive acidic etching agent. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse reflectance spectroscopy (DRS). The results showed that the products were composed of large amounts of polyhedron with hollow interior and porous surface. The as-synthesized AgCl@Ag HAs exhibited remarkable photocatalytic activity and excellent durability for the degradation of organic pollutants under visible light irradiation. The photocatalytic reaction followed the pseudo-first-order kinetics and the rate constant for the degradation of methyl orange (MO) photocatalyzed by AgCl@Ag HAs was 1.6 times that of the solid counterparts. The enhanced photocatalytic activity could be attributed to the hierarchical hollow morphology and unique porous structure, providing increased adsorption and enhanced light-harvesting efficiency. (c) 2013 Elsevier B.V. All rights reserved.