Ba_0.8Sr_0.2TiO₃/Poly (vinylpyrrolidone) (BST/PVP) composite fibers were successfully synthesized via electrospinning. The ceramic nanofibers were obtained after calcining the composite at 800 °C for 2 h. The morphology and structure of the BST fibers were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results reveal that the as-synthesized BST nanofibers show a diameter of 50–150 nm with the length over 0.1 mm, and a well-defined perovskite crystal structure. The electrical properties of the as-synthesized BST nanofibers were investigated through an impedance-type humidity sensor. The nanofibers exhibited excellent humidity sensing properties at room temperature. The possible sensing mechanism was proposed.