A water insoluble cucurbit[6]uril-polyoxometallates (CB[6]-POMs) composite assembled from alpha-Keggin type polysilicontungstate anions and macrocycle cucurbit[6]uril (CB[6]) via hydrogen bonding has been synthesized as visible light active photocatalyst. The physical and photocatalytic properties of such photocatalyst have been fully characterized by PXRD, FTIR, TG, XPS, and UV/vis diffuse reflectance spectra. The catalyst shows a good photocatalytic activity towards the degradation of methyl orange (MO) under visible light irradiation and displays good reproducibility of photocatalytic degradation by a simple recycled procedure without obvious loss in catalytic activity, which is of great significance for practical use of the photocatalyst. In the photodegradation process, the {Ni-CB[61]}(n) chain of the photocatalyst acts as sensitizer and can be induced by visible light, meanwhile the POMs chain of the photocatalyst acts as electron acceptor and deposits the electron in its LUMO. The effects of various experimental parameters and the proposed mechanisms are discussed in detail. (C) 2010 Elsevier B.V. All rights reserved.