A two-step hydrothermal process was employed to fabricate a highly efficient TiO2 film. In the first hydrothermal step, a bi-layer structure was synthesized, consisting of well-aligned one-dimensional (1D) rods and three-dimensional (3D) flower-like structures on an FTO substrate. Both morphologies exhibited a robust rutile phase, which is believed to provide direct conductive pathways and reduce electron-hole recombination. However, the compact nature of the bi-layer TiO2 structure limited dye absorption, resulting in suboptimal performance of Dye-Sensitized Solar Cells (DSSCs). To address this issue, an etching treatment using a highly acidic hydrochloric acid (HCl) medium was implemented as the second hydrothermal step. The samples’ morphology was carried out using field emission scanning electron microscopy (FE-SEM). A 4Point Probe (Signatone Pro4-440N) was connected to the source meter to ascertain the resistivity properties of the samples. The etching treatment effectively increased the surface area of the TiO2 bi-layer, facilitating improvements in DSSC performance. The etching process transformed the morphology into a needle-like structure as revealed by FESEM images, while the reduction in electrical resistivity indicated a significant enhancement in the material's properties. The etched sample demonstrated superior performance, achieving a power energy conversion (PEC) efficiency of 10.05%, compared to 6.41% for the non-etched sample.