Silica nanofibers were grown on the surface of chitosan nanofibers used as templates by coating the surface with silica derived from the hydrolysis and condensation of tetraethoxysilane using ammonium hydroxide as a catalyst. This was followed by the decomposition of the chitosan template. The relationship between different processing factors (type of templates as well as amounts of catalyst and template) and the formation of silica nanofibers was examined. Varying the processing factors was found to be effective in controlling the morphology of the silica nanofibers. The use of chitosan nanofibers effectively led to the formation of one-dimensional silica nanofibers as the positively charged chitosan nanofibers promoted the deposition of the negatively charged silica nanoparticles through electrostatic attractive forces. Therefore, the chitosan nanofibers acted as good deposition sites for interacting with silica nanoparticles. Although a large amount of catalyst promoted the sol-gel reaction, the silica nanoparticles grew excessively in the solvent. Therefore, the surface structure of the prepared silica nanofibers could be controlled by varying the amount of chitosan template as this also varied the formation mechanism of the silica nanofibers. The resultant samples had a rough silica wall composed of densely assembled silica nanoparticles, with a high specific surface area (338 m²/g).