Alumina fiber products have high modulus and strength that are resistant toward the attacks of molten metals and non-oxide materials up to 1000°C. Fibers also have low thermal conductivity and high melting point. In this work, alumina fibers were synthesized by sol-gel electrospinning technique (e-spinning). The sol was prepared by mixing aluminum nitrate nonahydrate (ALN) and aluminum isopropoxide at 1:3 molar ratios. The precursor sol was stirred vigorously for 24 hours until ALP completely dissolved. After stirring, the precursor sol with PVA and without PVA was evaporating to obtain the suitable viscosity to spin. The rheology and viscosity were checked by viscometer. At the appropriate viscosity range about 0.2 to 7 Poise, the sol was then spinning into fibers using electrospinning machine. The green fibers were then dried at room temperature then calcined at 1200°C. The fibers produced were characterized using X-Ray Diffraction (XRD) and Field Emission Scanning Electron Microscope (FESEM). The XRD analysis had shown the α-alumina was formed at 1200 °C and SEM micrograph shows the formation of fibers with PVA addition.