Hydroxyapatite (HAp) nanoscale fibers were produced by combining electrospinning and a sol-gel system. The fibers were electrospun from a mixture of polymer-calcium phosphate (CaP) sol, then subjected to heat treatment. XRD, FTIR, SEM and TEM with HRTEM analyses confirmed HAp nanofibers with the average fiber diameters varied from 80 to 110 nm can be produced. The effects of concentrations of CaP sol and thermal treatment on the structure of nanofiber were studied. Decreasing the concentration of sol in the mixture can produce HAp fibers with smaller diameters; while higher concentrations of the sol resulted in HAp ceramic fibers with porous structures. The possibility of using HAp nanofiber particles as a controlled release carrier of protein was examined. The amount of protein adsorbed onto HAp fibers decreased as the concentration of the sol and the temperature of heat treatment increased. The sustained release of Bovine serum albumin (BSA) from HAp nanofiber was observed. The study provides information relevant to the fabrication and bioapplication of ceramic nanofiber.