Nanocrystalline and porous barium titanate (BaTiO3) nanofibers with diameter 200-400 nm were synthesized via electrospinning and followed calcinations. The morphology and microstructure of the nanofibers were characterized using field emission scanning electron microscope, X-ray diffractometer and transmission electron microscope, respectively. And the electrical and humidity sensing properties of the nanofibers were also measured. The results reveal that the BaTiO3 nanofibers have a conductivity of about 0.3 S/cm, and show an ultrafast response time (~0.7 s) and a recovery time (~0.4 s) to humidity at room temperature. In addition, the sensing mechanism was also discussed briefly based on its nanocrystalline and porous microstructure of the electrospun material.