This study presents the synthesis of vanadium oxide nanowires via a simple hydrothermal method and explores their potential as high-performance sensors for monitoring harmful gases, with a particular focus on NO2. The microstructure and morphology of the nanowires were characterized using scanning electron microscopy, powder x-ray diffraction, and Raman spectroscopy. The vanadium oxide nanowire material demonstrates outstanding NO2 gas sensing capabilities, detecting 5 ppm with a rapid response and high sensitivity at an optimal working temperature of 150 °C. It exhibits a relative resistance change of 70%, showcasing a sub-ppm detection limit. The V2O5 nanowires exhibited good stability and high gas selectivity for NO2 over other interfering gases (H2S, NH3, C2H4, and CO). The ultrathin structure of the nanowires holds promise for practical applications in developing NO2 gas sensors. The study sheds light on the superior sensitivity of the V2O5 gas sensor toward NO2 at low temperatures, emphasizing the influence of the 1D structure on the sensing mechanism.