SiO2-supported MoP (MoP/SiO2) catalyst was prepared by using molybdenum acetylacetonate and ammonium hypophosphite as raw materials through wetness impregnation method, which was reduced at high-temperature reduction without calcination, The obtained MoP/SiO2 catalyst was characterized by XRD, N2-physisorptions, TEM and XPS to study the effect of P/Mo mole ratios (n(P):n(Mo)=1:1,2:1,3:1) in impregnation liquid and reduction temperature (500,550,600 ℃) on the formation of MoP phase. Its catalytic performance in the selective oxidation of benzyl alcohol to benzaldehyde was further investigated. It was found that the prepared MoP/SiO2 catalyst with P/Mo mole ratio of 2 and the reduction temperature of 550 ℃ (MoP/SiO2-550-2) had the highest conversion （99.7%）and selectivity（99.8%）in the selective oxidation of benzyl alcohol to benzaldehyde, which is attributed to the formation of more and small MoP phases on the MoP/SiO2-550-2 catalyst.