In this paper, the effect on coke formation of adding a Ni 0.75 Fe 0.25 catalyst layer to the anode side of a fuel cell running on methane is investigated. The formation of an intermediate FeNi 3 phase can be observed in catalysts annealed at different temperatures. The catalyst annealed at 705°C has the smallest calculated surface energy and grain size among all catalysts annealed at different temperatures. In addition, the O 2 -TPO profiles and Raman spectra of spent anode material reveal that the catalyst annealed at 705°C has the best coke resistance among all catalysts. Moreover, the cell with catalyst layer annealed at 705°C, under a current density of 600mAcm −2 at 650°C, experiences a decrease of 10% after operating in methane for 260min, which is much more stable than that without catalyst layer (a decrease of 50%).