The silicone-sheathed nanofibers based on ZnO-SiOx nanofibers transformed into Zn nanocrystal embedded polydimethylsiloxane (silicone) nanofibers by using electron-beam irradiation. Transmission electron microscopy (TEM) images showed that silicone-sheathed ZnO-SiOx nanofibers were synthesized during electron-beam irradiation of the calcined ZnO-SiOx nanofiber. High-resolution TEM image showed that the nanofibers were transformed into Zn nanocrystal embedded silicone nanofibers. The structural variation of the nanofibers was attributed to the evaporation and deposition of the silicone molecule and to the thermodynamic and double ionization effects during electron beam irradiation. The Zn nanocrystal embedded silicone nanofibers were formed due to the oxidation and the reduction due to the thermal and double ionization effects at the later stage of the electron-beam irradiation. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.050205jes]