We report a facile approach to perform post-growth doping of hematite (α-Fe2O3) nanostructures by depositing titanium (Ti) precursor solution and subsequent annealing in air. Using hematite nanowire photoanodes on fluorine doped tin oxide (FTO) glass substrates as a model system, the doping conditions were carefully optimized and highly photoactive hematite photoanodes were prepared at a more practically acceptable temperature of 650–700 °C than the ≥800 °C commonly used in previous works. A combination of microstructural characterization, elemental analysis, photoelectrochemical (PEC) measurements, and electrochemical impedance spectroscopy (EIS) analysis were employed to confirm the distribution of Ti atoms in hematite nanostructures and the role of Ti dopants in enhancing the photocurrent of hematite photoanodes. It was found that the Ti-treatment increases the donor concentration of hematite by about 10 fold and facilitates majority carrier transport and collection, which may account for the performance enhancement. Moreover, EIS measurements under illumination and Mott–Schottky analysis clearly showed that Ti dopants interact with the surface trap states of hematite, suggesting that surface passivation may also contribute to the improved PEC performance. This facile post-growth doping method can be applied to other hematite nanostructures such as electrochemically deposited hematite films and expanded to other dopants such as zirconium (Zr).