Over the last decades, there has been considerable interest in the synthesis of one-dimensional (1D) metal oxide nanostructures that can be used in gas sensor devices. Heterostructures, obtained by a combination of different semiconductor nanomaterials with different band energies, have been extensively studied in order to enhance their gas-sensing performance. In this context, our present study focuses on the investigation of chemiresistive-sensing capabilities of a combination of TiO2 nanoparticles and V2O5 nanowires obtained via hydrothermal treatment of the peroxo-metal complex. The formation of V2O5/TiO2 heterostructures was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) measurements. This study also proposes an efficient approach to produce 1D V2O5/TiO2 heterostructures with a good range of detection (0.09–1.25 ppm) and remarkable ozone-sensing properties related to repeatability and selectivity.