The catalytic activity of Fe/ZSM-5 for the selective reduction of NO to N2 with methane in the presence of excess O2 was studied. Fe/ZSM-5 catalysts with various Fe loadings were prepared by impregnation method. It is well known that methane is inactive when Fe/ZSM-5 as the catalyst for the selective catalytic reduction (SCR) of NO with methane. However, this paper shows that when the content of Fe was about 0.5%, Fe/ZSM-5 showed higher catalytic activity and selectivity of methane, and put forward measurable activation for CH4 is an important factor for the reaction of removal of NOx with CH4.