Barium titanate (BTO, BaTiO₃) nanofiber was prepared via electrospinning and followed annealing process. The as-spun and calcined BTO nanofibers were characterized by a scanning electron microscope (SEM). After annealing at 800 °C in air for 3 h, polycrystalline BTO nanofibers with 120-200 nm in diameter were successfully obtained. I-V characteristic curves of single BTO nanofiber were measured. The p-type semiconducting fiber shows a room-temperature conductivity of about 0.3 S/cm. In addition, the small humidity hysteresis demonstrates the application prospects of electrospun BTO nanofibers in the fabrication of a high-sensitive humidity sensor.