Modifications of the working electrode with TiO2 blocking or coating layers are carried by electrodeposition in TiCl3 precursor solution. The results suggest that the electrodeposited TiO2 blocking layer provides excellent agglutination between the FTO substrate and the active TiO2 layer. In addition, the electrodeposited TiO2 coating layer enhances the interconnections between the TiO2 nanoparticles and the FTO substrate, and therefore it increases the electron transport efficiency. The morphology and crystalline structure of the electrodeposited TiO2 layers are characterized by SEM, TEM, and XRD. The electrochemical impedance spectroscopy measurements show that the improved DSSC performance with the electrodeposited coating layer is mainly due to the increase in the lifetime of the conduction band electron in the TiO2 film. The photoelectron conversion efficiency of DSSC is increased from 3.47% to 5.38% by employing the TiO2 electrodeposited working electrode.