In this paper, we report the successful synthesis of Ni12P5 hollow spheres via a facile hydrothermal route, employing white phosphorus (WP) and nickel nitrate as the reactants in the presence of hexamethylenetetramine (HMT) and polyethylene glycol 10000 (PEG-10000). The phase and morphology of the product were characterized by means of powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). HMT and surfactant (PEG-10000) played important roles in the formation of Ni12P5 hollow microspheres. Furthermore. research also showed that the as-prepared Ni12P5 hollow spheres could photocatalytically degrade some organic dyes such as Safranine T and Pyronine B under irradiation of 365 nm UV light. (C) 2008 Elsevier Inc. All rights reserved.