Acidic mesoporous ZSM-5 zeolite (HZSM-5-M) and silica (SiO2) supported Ni2P catalysts (Ni2P/HZSM-5-M and Ni2P/SiO2) were prepared by incipient wetness impregnation method, and their catalytic performance was investigated in the selective hydrogenation of phenylacetylene. The supports and catalysts were characterized by XRD, N2-adsorption, NH3-TPD, H2-TPR, SEM and TEM techniques. The activity results show that phenylacetylene conversion on Ni2P/HZSM-5-M catalyst is 98.5%, while that on Ni2P/SiO2 catalyst is 45.6% at the reaction time of 2 h, indicating that the hydrogenation activity of Ni2P/HZSM-5-M catalyst is much higher than that of Ni2P/SiO2 catalyst. This feature could be due to the highly dispersed Ni2P phase with small particle size on the catalyst. In addition, the Ni2P/HZSM-5-M catalyst showed good repeatability.Ni2P/HZSM-5-M catalyst, as compare to Ni2P/SiO2 catalyst. The Ni2P phase with small particle size shows high hydrogenation activity, nevertheless, the influence of the particle size of the Ni2P phases on the styrene selectivity is not significant.