The p-type semiconductor Cu(I)-based delafossite transparent conducting oxides are good candidates to be used as hole collectors in dye-sensitized solar cells. The Al-doped CuGaO2 has been synthesized by hydrothermal method and its properties have been investigated as cathode elements in ruthenium dye N719-sensitized solar cells. The photocurrent density (J sc) and the open-circuit voltage (V oc) for 5% Al-doped CuGaO2 microparticles using N719 dye were approximately two times higher than undoped CuGaO2 microparticles. The integration of aluminum dopants in the delafossite structure improves the photovoltaic performance of CuGaO2 thin films, due to the excellent optical transparency of CuGaO2 in the visible range as well as the improved electrical conductivity caused by the apparition of the intrinsic acceptor defect associate (Al Cu •• 2O i ″ )″ with tetrahedrally coordinated Al on the Cu-site.