In the present research, the effect of ZnO-based blocking layers on the operational features of TiO2-based dye-sensitized solar cells is investigated. A facile solution-based coating method is applied to prepare an interfacial highly transparent ZnO compact blocking layer (CBL) to enhance the efficiency of dye-sensitized solar cells. Different precursor molar concentration were tested to find the optimum concentration. Optical and electrical measurements were carried out to confirm the operation of the CBLs. Morphological characterizations were performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) to investigate the structure of the compact layers. We have also developed a set of modeling procedures to extract the effective electrical parameters including the parasitic resistances and charged carrier profiles to investigate the effect of CBLs on the dye-sensitized solar cell (DSSC) performance. The adopted modeling approach should establish a versatile framework for diagnosis of DSSCs and facilitates the exploration of critical factors influencing device performance.