<p>This work addresses the challenge of fabricating transparent and conductive p-type titanium dioxide (TiO₂) and forming efficient p–n heterojunctions from the same material. The present work involves creating titanium voids in defective, undoped p-type TiO₂ films and utilises the melt-induction method to prepare p-type and n-type structures with varying morphologies. Transparent undoped defective p-type TiO₂ films were successfully synthesised by presenting native metal defects (titanium vacancies) and both the p-type and n-type TiO₂ films were prepared using the solvothermal method. The conductivity of both p-type and n-type TiO₂ films was confirmed in a previous work using Hall measurements. Field-emission scanning electron microscopy showed distinct nanostructures in each film; grass-shaped nanostructures for p-type TiO₂ and irregular grains for n-type. Titanium dioxide p–n homojunction was formed from transparent, non-negative p-type TiO₂ films with different growth times (9, 19, 24) h. The properties (<i>I</i>–<i>V</i>) of solid-state dye-sensitised solar cells (ss-DSSCs) based on the excited transparent p–n TiO₂ homojunction were measured. The photoelectric conversion efficiency of these ss-DSSCs varied with growth times, achieving values of 0.4, 1.8 and 1.38% for growth times of 9, 19, and 24&#xa0;h, respectively.</p>