Though nickel phosphides had been used widely to transform biomass into bio-fuel, the impact of support on the crystal formation was not clear. Herein, nickel and phosphides loaded on SiO2, ZSM-5 and ?-Al2O3 were synthesized and the interaction between Ni/P and the supports was studied. Pure Ni12P5 and pure Ni formed on SiO2 and ?-Al2O3, respectively, whereas the mixture of Ni12P5 and Ni formed on ZSM-5. The formation of AlPO4 species was the main factor for the absence of Ni12P5 on Ni/?-Al2O3 catalyst. Furthermore, the support also had a significant impact on the active phase with different particle size and dispersion, and further affected the performance. The highest fuel yield of 67.3 wt.% was obtained on Ni12P5/SiO2 catalyst, which might be attributed to the appropriate acid sites and proper Ni12P5 size. In addition, the catalysts with Ni12P5 crystal phase displayed good resistance to coke deposition. The findings are important for clarification of the role of support in nickel phosphide active phase formation and coke deposition.