In this paper, we report an alternate technique for the deposition of nanostructured TiO2 thin films using the electrohydrodynamic atomization (EHDA) technique using polyvinylpyrrolidone (PVP) as a stabilizer. The required parameters for achieving uniform TiO2 films using EHDA are also discussed in detail. X-ray diffraction results confirm that the TiO2 films were oriented in the anatase phase. Scanning electron microscope studies revealed the uniform deposition of the TiO2. The purity of the films is characterized by using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS), confirming the presence of Ti–O bonding in the films without any organic residue. The optical properties of the TiO2 films were measured by UV-visible spectroscopy, which shows that the transparency of the films is nearly 85% in the visible region. The current–voltage (I–V) curve of the TiO2 thin films shows a nearly linear behavior with 45 mΩ cm of electrical resistivity. These results suggest that TiO2 thin films deposited via the EHDA method possess promising applications in optoelectronic devices.