Biomorphic Al2O3 fibers have successfully been prepared using natural fibers of cotton as bio-templates. Cotton fibers are infiltrated with AlCl3 solution and subsequently sintered in air at high temperatures to produce the final Al2O3 fibers. The synthesized fibers faithfully retain the fibrous cotton morphologies, with the complete removal of the cotton body. The sintering temperatures adopted exhibit great effects on the surface pore-size distribution for the prepared Al2O3 fibers.