The performance of dye-sensitized solar cells (DSCs) was compared before and after processing the TiO2 electrodes by minute-order electrochemical reactions with metal nitrates, where the metals were Mg, Zn, Al, and La, in 2-propanol. An overcoating of metal hydroxide was formed without the need for a sintering process, and magnesium hydroxide was found to give the largest improvement in photovoltage, fill factor, and eventually overall conversion efficiency of the DSCs. To analyze the nature of the improvement, the diffusion coefficient (D) and electron lifetime (tau) were determined. While little influence of overcoating on D was seen, a correlation between the increase in tau and V-oc was observed for the metals examined here. The remarkable improvement in the electron lifetime of the DSCs suggests that an overcoating with magnesium hydroxide species function as the blocking layers at the fluorine-doped tin oxide and TiO2 interfaces, thus contributing to the suppression of electron leakage, i.e., recombination processes between unidirectional transporting electrons and polyiodides such as tri-iodide in the processed TiO2 photoelectrode systems. The increase in V-oc can be explained by the increased electron density caused by the increase in electron lifetime.