FePO4/SiO2 was employed for the oxidative bromination of methane (OMB) for the first time. A methane conversion of 50% and total selectivity of 96% for CH3Br plus CO (CH3Br:CO approximate to 1) were obtained at 570 degrees C. Comparison experiments were designed to investigate the roles of O-2, HBr and the catalysts. Powder Xray diffraction (XRD), X-ray photoelectron spectroscopy (XPS). Fourier-transform infrared spectroscopy (FTIR) and Fe-57 Mossbauer spectroscopic studies were conducted on the catalysts. It was confirmed that the FePO4 components of the fresh catalyst transformed quickly to stable active species during the induction period, and the active components of the stable catalyst have been found to consist of near-equimolar alpha-Fe-3(P2O7)(2) and Fe2P2O7. The reaction over the FePO4/SiO2 catalyst was proposed to follow a redox route based on the results of comparison experiments and associated characterization. (C) 2010 Elsevier Inc. All rights reserved.