Porous alumina nanofibers with hollow structure were fabricated by single capillary electrospinning of aluminum nitrate (Al(NO3)(3))/polyacrylonitrile (PAN) precursor solution, followed by sintering treatment. The Al(NO3)(3)/PAN composite nanofibers and sintered nanofibers were characterized by scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). It is found that the obtained alumina nanofibers show porous external surfaces and hollow sections. Upon sintering the composite nanofibers at 1300 degrees C, the nanofibers are consisted of alpha-phased crystalline grains. Sintering temperature plays an important role in controlling the morphology and crystal structure of the nanofibers. A mechanism based on "Kirkendall effect" was proposed to explain the formation process of the hollow structure. (C) 2013 Elsevier B.V. All rights reserved.