The thermal oxidation of evaporated titanium-vanadium thin films was carried out at different post-annealing temperatures. The structural, morphological, compositional, optical, electrical, and gas sensing properties of titanium-vanadium oxide thin films were primarily investigated. The results of the XRD study and Raman spectroscopy verified the presence of the orthorhombic V2O5, tetragonal TiO2, and monoclinic V2Ti3O9 phases. The crystallinity of TVO thin films was improved at higher annealing temperatures. The grain size (seen from SEM images) and oxygen compositions (obtained from EDS measurement) of TVO samples are also enhanced when the post-annealing temperature is increased from 500 to 575 °C. From the transmittance curves, the bandgap values for TVO samples were estimated and found in the range of 2.14–2.36 eV. The n-type conductivity of TVO films was confirmed by the negative Hall coefficient values. At last, the CO gas sensing response of TVO thin films was analyzed by monitoring the change in the surface electrical resistances at different operating temperatures and CO gas concentrations. The dynamic and static resistances were assessed at different operating temperatures varying from 100 to 300 °C. The TVO sample prepared at 550 °C showed the best conditions by examining the materials and CO sensing properties.