Electrostatic spinning is a well-developed technique for the fabrication of fibers in the nanoscale domain. Novel boron carbide nanofibers were generated by the electrostatic spinning and ceramic conversion of poly(norbornenyldecaborane) (PND) - a polymeric ceramic precursor. The prepyrolyzed fibers were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The ceramic fibers were characterized by SEM, X-ray diffraction (XRD), 11B magic-angle spinning nuclear magnetic resonance (MAS NMR) and DRIFT spectroscopy. SEM analysis showed retention of the nanostructure in the pre- and postpyrolyzed fibers.