SiO2, HZSM-5 and Al2O3 were used to support nickel phosphides to prepare hydrodeoxygenation (HDO) catalysts. The nickel loading was kept at 20 wt% while the Ni/P molar ratio was varied among 3, 2, and 1 in the preparation by incipient wetness impregnation. XRD characterization revealed that Ni3P, Ni12P5, and Ni2P as the major crystal phases were obtained at Ni/P ratio of 3, 2, and 1, respectively, on SiO2 and HZSM-5. When Al2O3 was used as the support, nickel metal rather than nickel phosphides was generated. Among SiO2-supported nickel phosphides, Ni3P exhibited highest hydrogenation activity and catalytic performance in phenol HDO. Ni3P/HZSM-5 showed the high catalytic performance in HDO of phenol as well as catechol and o-cresol, with Ni3P as the hydrogenation site and the acid sites in HZSM-5 zeolite as the dehydration site. The strong acidity in HZSM-5 also facilitated the isomerization of cycloalkanes at elevated temperatures.