The fibers of AlN were synthesized by carbothermal reduction and nitridation of precursor fibers obtained by electrospinning. XRD result indicated that the wurtzite AlN phase had been successfully synthesized in fibers. The SEM and TEM analysis indicated that the hollow fibers with an out-diameter of about 500 nm and a wall thickness of about 100 nm were obtained and the crystal in fibers was hexagonal after calcination. The fibers were further characterized by TG-DTA, FT-IR and UV-vis absorption spectra. The formation mechanism of hollow structure was proposed based on our understanding and characterizations. (c) 2008 Elsevier B. V. All rights reserved.