The Selective hydrogenation of nitrobenzene(NB) to aniline(AN) is an environmental friendly synthesis route, and its core is the efficiently selective hydrogenation catalyst. Herein, the amorphous Ni-Mo-P-Expanded Graphite(EG) catalysts were prepared by impregnation-chemical reduction method. Then, their selective hydrogenation catalytic performance was researched by the probe reaction above. After that, the catalytic properties of the samples were further investigated by X-ray diffraction(XRD), thermogravimetric analysis(TG), temperature programmed reduction (TPR), test of specific surface area and pore size distribution, etc. Finally, the results show that appropriate addition of expanded graphite could increase the specific surface area and stabilize the active species of the catalyst. Meanwhile, it could also increase the thermal stability and activity of the catalyst. The optimal addition of EG is 8 wt %, with the reaction temperature of 110 ℃, hydrogen pressure of 1.8 MPa and reaction time of 90 min, the conversion of nitrobenzene and selectivity of aniline reached 99.9%, respectively.