β-tricalcium phosphate (TCP) ceramic nanofibers via electrospinning route have been produced using β-TCP sol, which was prepared by the mixing of calcium nitrate tetrahydrate and triethyl phosphate as Ca sand P precursors, respectively. The as-prepared sol was tightly caped and aged in a drying oven at 90 °C for 16 hrs. The aged sol was evaporated in opened containers at 35 °C to reach a proper value of viscosity (100 cPs). Viscous solution was prepared by the mixing of β-TCP sol and high-molecular weight PVP to obtain appropriate viscosity for electrospinning. The mixed solution of β-TCP and PVP with various ratios were vigorously mixed using hot plate/stirrer for 24 hrs and then electrospun. The as-electrospun β-TCP nanofibers were dried in a drying oven at 60°C for 12 hrs and then heat-treated at 500, 600, 700 and 800 °C at 1°C/min heating rate in air. Surface morphology and phase identification of as-spun and heat-treated β-TCP nanofibers were studied. The results have shown that ratio between PVP and β-TCP sol and heat-treatment conditions significantly affected the crystalline phase and morphology of β-TCP nanofibers.