In this research we report the gas-sensing properties of TiO_2-x/TiO₂-based hetero-structure, which was ‘self-heated’ by current that at constant potential passed through the structure. Amperometric measurements were applied for the evaluation of sensor response towards ethanol, methanol, n-propanol and acetone gases/vapours. The sensitivity towards these gases was based on electrical resistance changes, which were determined by amperometric measurements of current at fixed voltage applied between Pt-based contacts/electrodes deposited on the TiO_2-x/TiO₂-based layer. X-ray diffraction (XRD) analysis revealed the formation of TiO_2-x/TiO₂-based hetero-structure, which is mainly based on Ti₃O₅/TiO₂ formed during the hydro-thermal oxidation-based sensing-layer preparation process. Additionally, photoluminescence and time-resolved photoluminescence decay kinetics-based signals of this sensing structure revealed the presence of TiO₂ mainly in the anatase phase in the TiO_2-x/TiO₂-based hetero-structure, which was formed at 400 °C annealing temperature. The evaluation of TiO_2-x/TiO₂-based gas-sensing layer was performed at several different temperatures (25 °C, 72 °C, 150 °C, 180 °C) and at these temperatures different sensitivity to the aforementioned gaseous materials was determined.