In this paper, we have developed a new strategy to construct the acidic sites on the surface of supported transition-metal phosphide catalysts, which could precisely control the deposition of the Al2O3 atomic layer through atomic-layer deposition (ALD). A series of supported nickel phosphide catalysts decorated with Al2O3 film were prepared and characterized. The results show that Al2O3 film was deposited on the surface of the catalyst via Al-O-Si bonding, which does not affect or alter the characteristics of the as prepared nickel phosphide phase. Most importantly, among all the Ni2P-based catalysts, the Ni2P/SiO2-ALD catalyst with 10 Al2O3 layers possesses the optimal performance in hydrodesulfurization and hydrodearomatization reactions. In particular, superior hydrogenation performances were considered to be strongly related to a synergistic effect between nickel phosphide and the modulated acidic property. This precise stepwise ALD strategy opens a convenient route and provides a prospective design guideline for constructing high-performance hydrogenation catalysts. (C) 2018 Elsevier Inc. All rights reserved.