The effects of TiO2 photoelectrode's surface morphology and different solvents on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were studied. By successive coating of TiO2 Suspension, composed of low and high molecular weight poly(ethylene)glycol (PEG) as a binder, double layered TiO2 photoelectrodes; with four different structures were obtained. Among the DSSCs with different TiO2 electrodes, DSSC with P2P1 electrode (P2 and P1 correspond to PEG molecular weights of 20,000 and 200,000, respectively) showed higher performance under identical film thickness at a constant irradiation of 100 mW cm(-2), which may be correlated with large pore size anti high Surface area of the corresponding TiO2 electrode. This was confirmed by electrochemical impedance spectroscopy (EIS) analysis of the DSSC and the transient photovoltage measurement of electrons in the TiO2 electrode. Among the different Solvents investigated here, the DSSC containing acetonitrile showed high conversion efficiency and the order of performance of the DSSCs with different solvents were AN>MPN>PC>GBL>DMA>DMF>DMSO. Better correlation was observed between the donor number of solvents and photoelectrochemical parameters of the DSSCs containing different solvents rather than the measured viscosity and dielectric constant of solvents. The reasons for the low performance of the DSSCs containing DMA, DMSO and DMF, respectively, were due to the negative shift of TiO2 conduction band and the desorption of dye molecules from the TiO2 photoelectrode by those solvents, (C) 2008 Elsevier B.V. All rights reserved.