Nitrogen-doped carbon (NDC) electron-donating materials were deposited on the surface of gamma-Al2O3 as hybrid supports and then loaded with active metals to obtain Fe-based catalysts for dibenzothiophene (DBT) hydro-desulfurization (HDS). The unique electron-donating-accepting behavior between NDC materials and Fe species not only enhanced the dispersion of the active metals, but also enhanced the sulfidation degree of Fe atoms and the subsequent HDS reaction in comparison to the pure gamma-Al2O3 supported catalysts. The HDS ratio of DBT at 400 degrees C improved from 36.9%-45.3% for pure FeSx catalysts, and from 92.9%-98.8% for Fe2Zn3Sx catalysts. Furthermore, it was found that the donation of electrons from N to sulfided Fe species tuned the electron structure, which improved hydrogenation (HYD) pathway selectivity.