A novel composite of Au-functionalized porous silicon (PS)/V2O5 nanorods (PS/V2O5:Au) was prepared to detect NO2 gas. PS/V2O5 nanorods were synthesized by a heating process of pure vanadium film on PS, and then the obtained PS/V2O5 nanorods were functionalized with dispersed Au nanoparticles. Various analytical techniques, such as field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), have been employed to investigate the properties of PS/V2O5:Au. Herein, the PS/V2O5:Au sample exhibited improved NO2-sensing performances in response, stability and selectivity at room temperature (25[Formula: see text]C), compared with the pure PS/V2O5 nanorods. These phenomena were closely related to not only the dispersed Au nanoparticles acting as a catalyst but also the p-n heterojunctions between PS and V2O5 nanorods. Whereas, more Au nanoparticles suppressed the improvement of response to NO2 gas.