A facile method was developed to synthesize a series of Fe-incorporated silica-pillared clays (denoted as Fe-SPCs) with various contents of Fe2O3. The synthesis was conducted under alkaline conditions using ethanol as the solvent containing the Fe source and dodecyl dimethyl benzyl ammonium chloride as the structure-directing agent. Characterization results showed that the Fe2O3 content of the Fe-SPCs was as large as 27.03 wt % and that all of the Fe-SPCs had a layered structure similar to that of the original SPC except that some silicone atoms in the tetrahedral coordination of the interlayered silica framework were replaced by Fe atoms. The Fe-SPCs showed excellent catalytic performance and reusability in the oxidative desulfurizations of both coking benzene and dibenzothiophene. A catalytical mechanism is proposed.