In this study, titanium dioxide (TiO2) was deposited onto a fluorine-doped tin oxide (FTO) substrate using the sol–gel spin coating method. Through the implementation of calcination treatment on the thin film, enhancements were observed in terms of structural, optical, and morphological properties. Various calcination temperatures were explored, with TiO2 annealed at 600 °C identified as the optimal sample. Analysis of the X-ray diffraction spectroscopy (XRD) pattern revealed the prominent orientation plane of (101), indicating the presence of anatase TiO2 with a tetragonal pattern at this temperature. Despite fluctuations in the optical spectrum, the highest transmittance of 80% was observed in the visible region within the wavelength range of 400 nm. The estimated band-gap value of 3.45 eV reaffirmed the characteristic of TiO2. Surface analysis indicated the homogeneous growth of TiO2, uniformly covering the FTO substrate. Cross-sectional examination revealed a thickness of 263 nm with dense and compact nature of TiO2 thin film. No presence of defects or pores reflects a well-organized structure and high-quality formation. Significant electrical rectification properties were observed, indicating the successful formation of a p–n junction. In summary, calcination treatment was found to be crucial for enhancing the properties of the thin film, highlighting its significance in the development of solar cell applications.