Dye-sensitized solar cells (DSSCs) have been intensively studied since their discovery in 1991. DSSCs have been extensively researched over the past decades as cheaper alternatives to silicon solar cells due to their high energy-conversion efficiency and their low production cost. However, some problems need to be solved in order to enhance the efficiency of DSSCs. In particular, the electron recombination that occurs due to the contact between the transparent conductive oxide (TCO) and a redox electrolyte is one of the main limiting factors of efficiency. In this work, we report for the first time the improvement of the photovoltaic characteristics of DSSCs by doping TiO2 with Al2O3. DSSCs were constructed using composite particles of Al2O3-doped TiO2 and TiO2 nanoparticles. The DSSCs using Al2O3 showed the maximum conversion efficiency of 6.29% due to effective electron transport. DSSCs based on Al2O3-doped TiO2 films showed better photovoltaic performance than cells fabricated with only TiO2 nanoparticles. This result is attributed to the prevention of electron recombination between electrons in the TiO2 conduction band with holes in the dye or the electrolyte. There mechanism is suggested based on impedance results, which indicated improved electron transport at the TiO2/dye/electrolyte interface.