A series of novel superior xFe-Ce-V catalysts were synthesized and systematically investigated for the first time on selective catalytic reduction of NOx by ammonium (NH3-SCR). Introducing Ce dramatically improved the catalytic activity, N2 selectivity, and H2O or/and SO2 resistance of FeVO4 in a broad operating temperature window of 150–400 °C, and the 0.75Fe-Ce-V exhibited the best de-NOx performance. Combined with XRD, TEM, XPS, NH3-TPD, H2-TPR, N2 ad-desorption, and in-situ DRIFTS results, the introduction of Ce not only increased the surface adsorbed oxygen, BET surface area, and redox ability, but also promoted surface acidic amounts. Moreover, the introduction of Ce also improved the formation of –NH2 intermediates, monodentate nitrite, and bridging nitrate, which were facilitated the NH3-SCR activity. The NO reduction was accomplished by both the Eley-Rideal and Langmuir-Hinshelwood mechanism (E-Rm and L-Hm) on catalysts. And the kinetic studies illustrated that the introduction of Ce enhanced the contribution of L-Hm in the NH3-SCR reaction. The above work pioneered the prospect of further exploring the novel and interesting NH3-SCR catalysts for NO reduction, and the 0.75Fe-Ce-V could be a potential practical application material in the de-NOx process.