The poly(acrylonitrile) (PAN) nanofiber web interpenetrated nylon-6 nanofiber supporters were prepared by electrospinning of an acrylonitrile (AN)/nylon-6 solution. It was realized that the average diameters of PAN and nylon-6 nanofiber were 20 and 100 nm, respectively, and that the PAN nanofibers constructed spider-mat networks which were supported by the robust nylon-6 nanofiber pillars. After stabilization and carbonization above 600 degrees C, both hollow-shaped and bamboo-shaped multi-walled carbon nanotubes (MWCNTs) were formed with the diameter range from 5 to 20 nm. The morphology and structure of MWCNTs had been further investigated by the combination techniques of transmission electron microscopy (TEM), electron diffraction (ED), X-ray diffraction (XRD) and elemental analyzer (EA).