The FTO/TiO2 interface plays a crucial role in the performance of dye-sensitized solar cells (DSSCs). The uneven microstructure morphology of FTO (luorine-doped tin oxide) glass surface and high porosity of T iO2 layer produce tiny gaps and voids at the FTO/TiO2 interface that breaks the connectivity, leading to an increase in the recombination process. In the current work, a dual functional passivating layer is introduced by the combination of the graphene/TiO2 compact layer. The excellent mobility and lexibility of graphene is capitalized using its layer to ill the voids in the FTO surface, which can consequently reduce the charge transfer resistance at the interface, while the added T iO2 compact layer avoids direct contact with the electrolyte thus reducing the recombination. Graphene was synthesized by the facile solvent exfoliation method with the assistance of the probe sonication process. The parameters of sonication were optimized to achieve high-quality concentrated graphene inks (0.177–0.51 mg/ml). Raman spectroscopy and transmission electron microscopy (TEM) revealed that the graphene obtained is of a few-layer type. Electrochemical impedance spectroscopy (EIS) analysis indicated that the incorporated compact layer of graphene/TiO2 was capable of accelerating the charge transfer and reducing the recombination process at the FTO/TiO2 interface. Consequently, the photoconversion eiciency (PCE) for the device (1 cm2 active area) with double-coated graphene layer under one sun irradiation (AM 1.5) was found to be 33% higher than the conventional one.