S-doped α-Fe 2 O 3 (α-Fe 2 O 3 /S) was synthesized with ferrous sulfate and Na 2 S 2 O 3 via a hybrid hydrothermal-calcination treatment. The crystal phase, special surface area, morphology of the α-Fe 2 O 3 /S as well as the chemical state of the sulfur were studied by X-ray diffraction (XRD), scanning electro microscopy (SEM), Raman spectrum and X-ray photoelectron spectroscopy (XPS). The Fenton and photo-Fenton reactivities of the α-Fe 2 O 3 /S were tested by degrading acid orange 7 (AO7) and phenol. Although α-Fe 2 O 3 /S showed little Fenton reactivity in the dark, it had an excellent heterogeneous Fenton reaction under either UV or visible irradiation, while other α-Fe 2 O 3 s were still kept inactive. S element was found to dope into α-Fe 2 O 3 in the forms of FeS or FeS 2 in α-Fe 2 O 3 /S. The doped S element promotes the photo-Fenton reaction of α-Fe 2 O 3 /S via two roles: retarding the recombination of photogenerated charge carriers and promoting the electron transfer between the peroxide species and iron ions at the interface.