Zinc oxide (ZnO) nanofibers were synthesized by atom layer deposition (ALD) using polyvinylpyrrolidone (PVP) fibers as template. It was found that the morphologies of ZnO nanofibers were the same as PVP nanofibers. By annealing treatment, the different morphologies of ZnO nanofibers could be formed with the decomposition of PVP nanofibers which were characterized by means of transmission electron microscopy (TEM) and room temperature Raman spectra. The crystal and the optical properties can be also improved. The photocatalytic activities of the as-growth ZnO samples were evaluated in the photocatalytic degradations of aqueous solutions of methyl orange at room temperature. ZnO nanofibers showed higher photocatalytic activity due to more surface-to-volume ratio. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.