A series of hydrogenation catalysts with γ-Al2O3 and phosphorus-modified γ- Al2O3 as the carrier and Ni and W as the active metal components were prepared by the equal volume impregnation method. The supports and catalysts were characterized with N2 adsorption-desorption, XRD, NH3-TPD and Py- IR. The phosphorus modification effects on the properties of hydrogenation catalysts were examined, and the relationship between adsorption behavior of quinoline, indole, dibenzothiophene(DBT) and the catalysts properties as well as the properties of the adsorbate itself were investigated. The results indicated that quinoline was the most easily adsorbed on Al2O3 catalysts and phosphorus-modified Al2O3 catalysts, while the adsorption capacity of indole and DBT was almost the same. The catalysts modified by phosphorus showed smaller specific surface area and pore volume, but on which the adsorption capacity of quinoline, indole and DBT was promoted. The adsorption capacity of sulfur and nitrogen compounds on the catalysts increased with the increase of the catalyst surface acidity or the acid site quantities and the increase of the active metal dispersion, as well as the increase of the heteroatom electron cloud density or molecular polarity of the sulfur and nitrogen compounds.