Bulk and SiO2 supported iron phosphide (FeP) samples were synthesized with a mixture of iron sulfide (FeS) and sodium hypophosphite (NaH2PO2 center dot H2O). The physical and chemical properties of the as-prepared FeP/SiO2 were studied by X-ray powder diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and thermal gravimetric analysis. Dibenzothiophene was effectively hydrodesulfurized over the as-synthesized FeP/SiO2 (Fe: 10 wt.%). The as-prepared FeP/SiO2 shows a higher activity than the FeP/SiO2 obtained by the temperature-programmed reduction route. The Fe-P-S species constructed in situ may be responsible for the higher activity. The method is also feasibly applicable in synthesizing other transition metal phosphides. (C) 2015 Elsevier B.V. All rights reserved.