As an alternative to noble metal hydrogenation catalysts, pure molybdenum carbide displays unsatisfactory catalytic activity for arene hydrogenation. Precious metals such as palladium, platinum, and gold are widely used as additives to enhance the catalytic activities of molybdenum carbide, which severely limits its potential applications in industry. In this paper, iron-promoted molybdenum carbide was prepared and characterized by various techniques, including in situ XRD, synchrotron-based XPS and TEM. while the influence of Fe addition on catalytic performance for toluene hydrogenation was also studied. The experimental data disclose that a small amount of Fe doping strongly enhances catalytic stability in toluene hydrogenation, but the catalytic performance drops rapidly with higher loading amounts of Fe.