In recent years, nickel based nanomaterials have attracted much attraction owing to their low cost and the unique catalytic properties in some special reactions. Uniform diameter polymethyl methacrylate (PMMA) nanofibers and beta-cyclodextrin (beta-CD) functionalized PMMA nanofibers were obtained through electrospinning. Nickel-loaded nanofibers (Ni/beta-CD/PMMA) were prepared by a reductive impregnation method. With increasing addition of beta-CD, the diameter of the composite nanofibers became larger. The images by scanning electron microscopy (SEM) suggested that the morphology for different beta-CD loadings of the beta-CD/PMMA nanofibers was uniform until the loading of beta-CD was 8 wt.%; the morphology of the nanofibers then became nonuniform and nodes appeared. Energy dispersive spectrometry (EDS) revealed that the Ni nanoparticles were loaded on the surface of nanofibers successfully.