Molybdenum - tungsten oxide (Mo_1-xW_xO₃, x = 1, 0.8, and 0.6) nanostructured thin films-based room temperture (RT) gas sensors are prepared by means of reactive RF magnetron co-sputtering at 400 °C. The structural, morphology, topography, optical, and electrical characterizations of the prepared sensors are carried out by XRD Rietveld structure refinement analyses, SEM, AFM, UV-VIS spectrophotometer, and source meter. By controlling the deposition temperture of 400 °C, a co-existing phase of MoO₃ and MoO₂ in WO₃ matrix is presented with high oxygen vacancies concentration as calculated from the XRD Rietveld Refinement analyses. By increasing the Mo content, the calculated oxygen vacancies concentration increases by factor of 1.36. The optical characterization of Mo_0.2W_0.8O₃ thin film shows a high transparent of 99.6% at 500 nm. The prepared thin films have successfully tested to detect carbon dioxide (CO₂) at RT (20 °C) with high selectivity and repeatability. The Mo_0.4W_0.6O₃ sensor film shows an electrical Schottky contact with fast response and recovery times towards CO₂ under UV light activation. Mo_0.4W_0.6O₃ thin film under dark and UV conditions were able to detect low CO₂ concentration of 2 and 0.5 sccm CO₂ at RT, respectively. Under UV illumination, Mo_0.4W_0.6O₃ film shows a fast response and recovery time of 6.53 and 8.05 s at 0.5 sccm with sensitivity of 29.19%. Under UV photonic activation, higher electron concentration is presented in the oxide surface, which leads to high probability for reaction with CO₂ molecules, and consequently enhanced the chemisorption of CO₂. The enhanced CO₂ gas sensitivity and fast response may refer to the high oxygen vacancies concentration and the active role of the grain boundaries in MoO₂, MoO₃ and WO₃ mixed-valence nanostructured under UV activation.