Application of electrspun TiO2 nanofibers was reported for an electrode for dye-sensitized solar cells (DSSC). This paper reports on structural characterizaion and morphology of titanium dioxide (TiO2) nanofibers prepared by electrospinning using a solution that contained poly (vinyl acetate) (PVAc) and titanium (IV) isopropoxide (Tip) and acetic acid as a catalyst for sol-gel reaction in dimethyl formamide (DMF). TiO2 nanofibers with diameters of 80-100 nm were successfully obtained from calcination of the as-electrospun TiO2/PVAc composite nanofibers at above 400˚C in air for 5hr. The as-electrospun and calcined TiO2IPVAc composite nanofibers were characterized by SEM, XRD, FT-IR, TGA, BET. The results indicated a significant effect of calcination temperature on the crystalline phase in the form of either anatase or mixed anatase-rutile and the morphology of the nanofibers.