Highly active Ni2P catalyst supported on Al2O3@TiO2 (core@shell) for hydrodeoxygenation (HDO) of benzofuran (BF) was described. The effect of the TiO2 shell thickness on the structure and HDO properties of Ni2P/Al2O3@TiO2 was studied. The results showed that an appropriate TiO2 shell thickness can effectively suppress the formation of AlPO4 and change the transmission mechanism of Ni2P particles, which is beneficial to the formation of highly dispersed Ni2P particles on the Al2O3 core. The Ni2P/A@T-25 showed the best HDO activity of 95% with oxygen-free products yield of 87% among the as-prepared Ni2P/Al2O3@TiO2 catalysts. As compared with Ni2P/Al2O3 (BF conversion of 78% with oxygen-free products yield of 47%), the BF conversion and yields of oxygen-free products over Ni2P/A@T-25 catalyst were increased by 22% and 85%, respectively.