Silica nanowires (NWs) were prepared on the Si wafer with a modified thermal evaporation of silicon monoxide and cryptophane-A was fixed to the surface of the silica NWs for methane sensing. Scanning electron microscopy equipped with EDS was used to characterize the morphology and composition of the sensitive material. A fiber optical device was designed to operate via luminescence reflection and the methane sensing properties were characterized at room temperature. The sensing material shows a stable and strong blue luminescence when excited by UV light source at wavelength of 380 nm, and it is efficiently quenched by molecular methane within the methane concentration range between 0.2% and 3.5% (v/v). This novel methane sensing material has significant advantages and might have application potential.