A method for preparation of silica nanowires with dimensions of d = 10-100 nm, 5-500 nm, is described. The nanostructured material is an integral part of the inner surface of narrow bore fused-silica capillary tubing. The wire preparation method is based on a decomposition of 2-chloro-1,1,2-trifluoroethyl methyl ether at elevated temperature and pressure. The silica bulk material is rearranged via a sustained silica-hydrogen fluoride chemistry, and reaction mechanisms for this process are proposed. The method is suitable for preparing long lengths of tubing with the modified surface. It is our belief that the texture of the capillary wall with its increased surface area is useful for applications such as microreactions, catalysis, and high-resolution pressure and/or electrodriven open-tubular liquid chromatography.