We report the results of the ambient pressure synthesis of tungsten oxide nanowires and nanoparticles on AlN substrates using the hot filament CVD techniques. The morphologic surface, crystallographic structures, chemical compositions, and bond structures of the obtained samples have been investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDX), and Raman scattering, respectively. Different morphologies were observed for different substrate temperatures, but otherwise identical growth conditions. The experimental measurements reveal the evolutions of the crystalline states and bond structures following the substrate temperatures. Besides, different substrate materials also affected the tungsten oxide nanostructures. Bundles of wire‐type tungsten oxide nanowires with a length of up to 5 mm were obtained on Al2O3 substrate. Furthermore, the sensitive properties of the super long nanowires to the gas and different temperature were investigated. The dependence of the sensitivity of tungsten oxide nanowires to the methane as a function of the time was obtained. The sensitive properties of the tungsten oxide nanowires have almost linear relationship with the temperature.