Polyoxometalate–TiO₂ composites have been successfully introduced into the photoanode of dye-sensitized solar cells to reduce the recombination of the electrons, which results in a longer electron lifetime. The performance of the cells with the polyoxometalate-modified photoanode is better than the cell with a pure P25 photoanode. The effect of the polyoxometalate was studied by electrochemical impedance spectroscopy and open-circuit voltage decay measurement. The results show that the electron lifetime becomes longer following an increase in the amount of the polyoxometalate.