Barium titanate (BTO) nanofibers were synthesized by electrospinning and followed calcination. The morphologies and microstructures of the nanofibers were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Calcinating temperature and process greatly influenced the surface morphology of the nanofibers. In addition, parallel BTO nanofibers were also successfully produced by a centrifugal electrospinning technique. And the humidity sensing properties of the nanofibers were measured. The results showed an ultrafast response time (similar to 0.5 s) and a recovery time (similar to 0.4 s) to humidity at room temperature, which revealed excellent humidity sensitivity performance.