Three kinds of bulk iron phosphates were prepared via different methods and employed as model catalysts in the oxy-bromination of methane (OBM). Na3Fe2(PO4)(3) was obtained via a fluoride route for the first time that showed even superior catalytic performance than FePO4. Phase evolution from Na3Fe2(PO4)(3) to Na2Fe3(PO4)(3) after the OBM was confirmed both by X-ray diffraction and Fe-57 Mossbauer spectroscopy. Temperature-programmed reduction of hydrogen and desorption of CH3Br revealed that the redox capacity of iron phosphates were responsible for the generation of bromine radicals on catalyst surfaces while CH3Br-involved reactions likely belonged to gas-phase reactions. Model iron phosphate catalysts were synthesized by three different methods. It was found that the Na3Fe2(PO4)(3) catalyst prepared by a fluoride route showed superior OBM performance than the other two catalysts both with the phase of FePO4, especially for producing higher CH3Br selectivity.