In this paper DSSCs of various electrode thicknesses (L = 3 µm→12 µm) are assembled using N719 dye, an iodide (I " )/triiodide (I # " ) redox liquid electrolyte and TiO2 (P-25) working electrode (WE). The theoretically modeled equations defining various bulk and interface impedances are incorporated with EIS spectrum analyzer software to fit the simulated EIS curves with experimentally measured EIS curves to evaluate the charger transfer and recombination properties of the assembled DSSCs. EIS fitting parameters investigated to study the impact of WE thickness on the charge transport properties of assembled DSSC. It is observed that the charger transfer resistance at TiO2/electrolyte interface (Rk) and series resistance (Rs) are reduced from 8 Ωcm 2 → 4.05 Ωcm 2 and 14.5 Ωcm 2 →10.06 Ωcm 2 respectively which shows consistency with improvement in electron life time (τe) from 5.8 ms →12.4 ms for increasing WE thickness, L = 3 µm→12 µm. The combined impact of significant reduction in Rk and Rs along with improved trend of τe can be considered as major factors for efficient electron injection across Dye/TiO2 interface hence increases short circuit current (Isc) from 1.485 mA → 2.365 mA and photovoltaic conversion efficiency (η) from 3.55 % → 5.46 % for L = 3 µm→12 µm, respectively. Moreover, a remarkable increment in η (~45%), τe (~56.3%) and a noticeable reduction in Rk (~38.75 %), Rs (~23.8 %) are observed for WE variations (L = 3 µm→6 µm) and further shows insignificant change for thicker WE (L> 6 µm). EIS technique is successfully applied to understand the detailed mechanism of charge transport and hence to extract the DSSC parameters which enable us to optimize the cell performance.