In this work, we report for the first time the improvement of the photovoltaic characteristics of dye-sensitized solar cells (DSSCs) by doping TiO2 with Fe2O3. DSSCs were fabricated using various percentages of Fe2O3-doped TiO2 composite nanoparticles. The Fe2O3-doped DSSCs exhibited a maximum conversion efficiency of 5.76% because of the effective electron transport. DSSCs based on Fe2O3-doped TiO2 films showed better photovoltaic performance than cells fabricated with only TiO2 nanoparticles. This result was attributed to the prevention of recombination between electrons in the TiO2 conduction band with the dye or electrolytes. A mechanism was suggested based on impedance results, which indicated improved electron transport at the interface of the TiO2/dye/electrolyte.