The effect of hydroxyl group attachment on the nanocrystalline TiO2 photoelectrodes for the performance of dye-sensitized solar cells (DSSCs) was investigated. The photoelectrodes were prepared using commercial TiO2 nanoparticles (Degussa P25). Hydroxyl groups were attached to the TiO2 film using hydrogen peroxide by thermal treatment method and the OH-attached sample was compared with the untreated one. The FTIR spectra evidenced the presence of hydroxyl groups attached to the TiO2 nanoparticles. Thermogravimetric analysis showed that the sample treated with hydrogen peroxide was attached with higher weight percentage of hydroxyl groups. The photovoltaic characteristics of the as-prepared DSSCs were measured by an electrochemical analyzer under the standard AM 1.5 illumination of 100 mW/cm2 light source. The hydroxyl groups attached sample showed an enhanced performance of DSSC than that of the blank P25 film. It shows that higher amount of dye was adsorbed due to the surface hydroxyl groups on the H2O2-treated samples. Electrochemical impedance spectroscopy (EIS) measurement indicated that the electron lifetime for the H2O2-treated sample was longer than that of the untreated sample. The higher dye loading due to the attached hydroxyl groups on the sample was confirmed using UV-vis measurement.