BaTiO3 (BTO) nanofibers were fabricated by sol-gel combined with electrospinning method. The effects of the concentration of acetic acid and sintering temperatures on the crystal phase and microstructure of the samples were investigated by scanning electron microscopy, X-ray diffraction, and transmission electron microscopy (TEM). BTO nanofibers with improved surface morphology were obtained as the ethanol to acetic acid ratio (E/A) was 8:3. The fibers calcined at 750 degrees C for 2h exhibited good morphology and crystallization. TEM studies revealed that the BTO nanofibers were polycrystalline, with diameters being on the order of hundreds nanometer, where the existence of domains offered proof of ferroelectric structure. The ferroelectric domains and piezoresponse of BTO nanofibers were characterized by piezoresponse force microscopy. The calculated d(33) was 20pm/V at maximum strain amplitude.