TiO2 has been used in various fields such as solar cells, dental implants, and photocatalysis, because it has high physical and chemical stability and is harmless to the body. TiO2 nanofibers which have a large specific surface area also show a good reactivity in bio-friendly products and excellent photocatalysis in air and water purification. To fabricate TiO2 nanofibers, an electrospinning method was used. To observe the diameter of TiO2 nanofibers with fabrication variables, the fabrication variables was divided into precursor composition variables and process variables and microstructure was analyzed. The concentrations of PVP (Polyvinylpyrrolidone) and TTIP (Titanium(Ⅳ) isopropoxide) were selected as precursor composition variables, and inflow velocity and voltage were also selected as process variables. Microstructure and crystal structure of TiO2 nanofibers were analyzed using FE-SEM (Field emission scanning electron microscope) and XRD (X-ray diffraction), respectively. As-spun TiO2 nanofibers with an average diameter of about 0.27 μm to 1.31 μm were transformed to anatase TiO2 nanofibers with an average diameter of about 0.22 μm to 0.78 μm after heat treatment of 3 hours at 450ºC. Anatase TiO2 nanofibers with an average diameter of 0.22 μm can be expected to improve the photocatalytic properties by increasing the specific surface area. To change the average diameter of TiO2 nanofibers, the control of precursor composition variables such as concentrations of PVP and TTIP is more efficient than the control of electrospinning process variables such as inflow velocity and voltage.