Using impregnation technique, a small amount of Rh(III) clusters has been grafted on the BiOCl microflowers. The samples are characterized by X-ray diffraction, scanning electron microscopy coupled with high energy distribution X-ray, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activities are investigated by the decomposition of gaseous acetaldehyde under irradiation of visible light. The bare BiOCl microflowers exhibit the limited visible light photocatalytic activity because of its wide band gap. After surface modification of Rh(III) clusters, the Rh(III)-BiOCl samples show an enhanced photocatalytic activity for the decomposition gaseous acetaldehyde under visible light irradiation. It is found that the Rh(III) clusters play an important role for the visible light absorption, probably through the electron transfer between Rh(III) clusters and the BiOCl, as well as the redox reaction centers for the multi-electron reduction of O-2. (C) 2016 Elsevier B.V. All rights reserved.