An interesting boron nitride ceramic was introduced in nanofibrous form. Boron nitride nanofibers were prepared using a simple and cheap strategy. Calcination of poly(vinyl alcohol) electrospun nanofibers embedded with boron nitride nanoparticles resulted in a nanofibrous form. The electrospun nanofiber mats were prepared by electrospinning of a colloidal solution composed of an aqueous poly(vinyl alcohol) solution and boron nitride nanoparticles. Calcination of the obtained BN/PVA nanofiber mats in an argon atmosphere at 1,000 degrees C for 5 h resulted in boron nitride nanofibers. The boron nitride nanofibers showed a higher band gap than the nanoparticles; the latter showing a band gap of 2.75 eV. however, the nanofibrous shape enhanced the band gap to 4.52 eV.