SnAlPO4-5 molecular sieves were hydrothermally synthesized using SnCl2 center dot 2H(2)O as the tin source, and were verified that divalent tin was incorporated into the framework by isomorphous substitution of trivalent aluminum, and increasing the numbers of Bronsted and Lewis acid sites relative to those in AlPO4-5. The molecular sieves were used to fabricate hybrid supports with alumina and then were loaded with active metals to obtain NiW catalysts. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) were evaluated for the catalytic activity of the catalysts. Because of the higher number of weak acid sites, much greater average number of slab layers and higher dispersion of WS2, the HDS rate of DBT at 280 degrees C is improved from 49.6% for the NiW/(AIPO(4)-5 + Al2O3) catalyst to 82.2% for the NiW/(Sn0.12AlPO4-5 + Al2O3) catalyst. Moreover, the highly active NiW/ (Sn0.12AlPO4-5 + Al2O3) catalyst obviously increases the product of the direct desulfurization route in the DBT HDS, which is beneficial for reducing hydrogen consumption in the industrial applications.