Mixture of polylactide (8 wt%), zinc acetate (6 wt%) and hexafluoroisopropanol was first used as electrospinning solution to fabricate ZnO nanofibers. Unfortunately, after direct calcination of the precursor polylactide/zinc acetate nanofibers, only ZnO film was prepared. Surprisingly, when the precursor fibers were pre-hydrolyzed with NaOH, ZnO nanofibers with diameter of 678 nm were obtained. The mechanism analysis showed that the preserve of fiber structure was attributed to the formation of zinc polylactic acid in the process of hydrolyzation. After characterized by scanning electron microscope and transmission electron microscope, the ZnO film was found to be an aggregation of irregular nanoparticles and the ZnO nanofiber was a necklace-like arrangement of cylindrical grains. X-ray diffraction and photoluminescence measurements indicated that the crystalline quality of the ZnO nanofibers was higher than the film. Furthermore, photocatalytic performance of the ZnO samples was investigated. Comparing with ZnO film, ZnO nanofibers exhibited much higher activity. (C) 2014 Elsevier B.V. All rights reserved.