ZrO2/SiOx core/shell nanofibers with diameter similar to 50 nm were synthesized by the thermal oxidation of ZrSi2 substrates with gallium. The crystalline ZrO2 cores were grown with amorphous SiOx shells. It is proposed that the growth of crystalline ZrO2 core was guided by the prior supersaturation of Zr species in the molten gallium film, whereas the amorphous SiOx shell could be attributed to the deposition of SiO vapor on the surface of ZrO2 core. In addition, the ZrO2/SiOx core/shell nanofibers show a wide visible photoluminescence (PL) emission at 480 nm, which should originate from the SiOx shells. (C) 2011 Elsevier B. V. All rights reserved.