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Hematite (α-Fe2O3) has been extensively studied as a promising candidate for photoelectrochemical water splitting; however its overall efficiency is still relatively low. Doping is believed to be efficient in enhancing the photoactivity, while direct evidence for the promoted charge carrier dynamics is very limited. Herein, transient absorption spectroscopy was used to directly investigate the yield and decay dynamics of the photogenerated holes in Sn and/or Ti doped α-Fe2O3. Sn or Ti doping was observed to have different origins to the enhanced water oxidation photocurrent: Sn doping retarded the electron-hole recombination, while Ti doping mainly increased the photogenerated charge carrier density. Our results also demonstrated that co-doping may combine both advantages to enhance the overall photoactivity of α-Fe2O3.