In this study, the photoelectrochemical characteristics of a ruthenium photosensitizer with an alkyl bithiophene group, designated as CYC-B1, are studied. The effect of mesoporous TiO2 film thickness on the photovoltaic performance of CYC-B1 and N3 dye sensitized solar cells was investigated. The performance of the DSSC fabricated using CYC-B1 dye anchored TiO2 photoelectrode showed a convincing enhancement in cell efficiency when the TiO2 film thickness was increased from 3 μm (eff.=5.41%) to 6 μm (eff.=7.19%). The efficiency of the CYC-B1 sensitized DSSC was maximum at 6 μm of the TiO2 film thickness, reached its limiting value and remained constant up to 53 μm, although a similar trend was also observed for N3 dye sensitized DSSC, however, the maximum efficiency achieved was at 27 μm thickness (eff.=6.75%). The effect of guanidinium thiocyanate (GuSCN) (additive) addition to the electrolyte on the photovoltaic performance of DSSCs based on CYC-B1 was also investigated. Furthermore, the electrochemical impedance spectroscopy (EIS) technique and photo-transient laser method have been employed to analyze the charge transfer resistances (R ct) and the lifetime of the injected electrons on the TiO2 containing different thicknesses.