Silica nanofibers containing silver nanoparticles were successfully prepared using sol-gel chemistry and electrospinning technique. Solution of tetraethly orthosilicate in ethanol containing silver nitrate was aged to have sufficient viscosity and electrospun to form nanofibers. Upon thermal treatment, the gelation reaction between silanols was completed in the prepared silica nanofibers, and at the same time, silver ions in the nanofiber changed to metallic silver or silver oxides. The reduction of silver ions could be also achieved by UV irradiation, and the generated silver nanoparticles were present preferentially on the surface of the silica nanofibers. On testing release behavior of silver ions, it was found that most of silver remained in the silica nanofiber. The silica nanofibers containing silver nanoparticles exhibited excellent antibacterial and deodorant properties.