The citric acid/nickel acetate composite hollow fibers were prepared by using sol-gel processing and co-electrospinning technique. The polycrystalline NiO hollow nanostructured fibers were prepared after calcination. The obtained hollow nanostructured fibers made up of 1725 nm nanocrystals were about 150nm to several micrometers in outer diameter. The hollow NiO nanostructured fibers have been characterized by TG, DSC, SEM, FTIR, and XRD techniques. The results showed that the morphology of NiO hollow fibers was obviously influenced by the calcination temperature.