Nano-scale hydroxyapatite particle network with uniform morphology and good crystallinity was fabricated on silica fiber by using carbon nanofibers as templates and with a methanol solution of Ca(NO3)2 x 4H2O-H3PO4. Field emission scanning electron microscopy, coupled with X-ray diffraction analysis confirmed the template effect and the existence of hydroxyapatite on silica fiber. It was clearly verified that by tuning the formation of carbon nanofibers on silica fiber, it was possible to control the properties of the resulting hydroxyapatite on silica fiber. In addition, the formation mechanism of hydroxyapatite on silica fiber via the template route was proposed.