Cyclic voltammograms for titanium-doped α-Fe2O3 electrodes in 0.1 M NaOH exhibited small reduction and re-oxidation peaks negative of -0.4 V (s.h.e.) and for electrodes initially held negative of this potential, the onset of the photocurrent occurred at potentials well positive of Vfb. These results are interpreted as due to the penetration of hydrogen into the lattice. The activity for oxygen reduction increased with dopant concentration and plots of steady-state log i against V exhibited slopes of absolute value approximately 2RT/F negative of Vfb, >2RT/F for Vfb < V < 0.3 V and < 2RT/F at more positive than 0.3 V. No oxygen reduction current was observed for oxygen partial pressures less than c. 0.45 atm. This effect was independent of electrode potential, dopant concentration and almost independent of pH. The results are interpreted in terms of the step O2 + H20 + e- → HO2(ad)+ OH- being rate-determining with titanium donors mediating change transfer.