Electrospinning is a versatile and straight forward process for synthesizing one-dimensional (1D) nanostructures of diverse materials. Recently, a large variety of oxide ceramics have been synthesized in combination with conventional sol-gel processing. Here, the synthesis of BaTiO3 nanofibers via electrospinning is reported. The structural evolution from amorphous to crystalline is presented under various heat treatment conditions. Nanofibers with well-defined perovskite tetragonal phase were achieved with an average crystallite size of about 20 nm. Furthermore, single crystalline BaTiO3 nanofibers with 50 nm in diameter and lengths up to 1 mu m were found, which is a novelty in electrospinning of ferroelectrics. XRD peak splitting confirmed the tetragonal perovskite structure, and this was fully supported by further evidence from selected area electron diffraction and Raman spectroscopy.