Large quantities of silica nanowires were synthesized through thermal treatment of silicon wafer in the atmosphere of N(2)/H(2)(5%) under 1200 °C with Cu as catalyst. These nanowires grew to form a natural bright-white mat, which showed highly diffusive reflectivity over the UV-visible range, with more than 60% at the whole range and up to 88% at 350 nm. The utilization of silica nanowires in diffusive coating on the reflector cup of LED is demonstrated, which shows greatly improved light distribution comparing with the specular reflector cup. It is expected that these nanowires can be promising coating material for optoelectronic applications.