<p>The doctor blade method has been applied for the deposition of thin films of V₂O₅ and Li_xV_2−xO₅ on indium tin oxide (ITO) substrates to study the electrochromic enhancement and photovoltaic processes. Atomic force microscopy demonstrates that varying the Li-ion doping concentration modifies the surface morphology of V₂O₅ and reveals irregularly distributed hillock islands, as well as a decrease in surface roughness and root mean square (RMS) roughness from 579.4 nm to 224.7 nm and from 677 nm to 231 nm, respectively. Chronoamperometric analysis is performed in the range of −1.0 V to 1.0 V with a time interval of 30 s, and coloration is determined through transmittance spectra for the electrochromic application. The optical density is increased from 0.3109 to 0.3257, which shows coloration efficiency (CE) of 67.88 cm² C⁻¹ and 69.32 cm² C⁻¹ for L0.4VO and L0.6VO specimens, respectively. L0.8VO shows a slight decrease in CE. The current–voltage (<i>I–V</i>) characteristics are also determined for the LVO and V₂O₅ thin film electrodes prepared by the in situ doctor blade method on the ITO substrate. The open-circuit voltage (<i>V</i>_oc) and short-circuit current density (<i>J</i>_sc) are recorded, varying from 1.98 V to 2.00 V and 10.26 mA cm⁻² to 24.45 mA cm⁻², respectively The power conversion efficiency (PCE) and fill factor (FF%) are approximately 10.93% and 58.98%, showcasing the highest value for L0.6VO thin film.</p>