Novel In 1.94 Sn 0.06 O 3 (ITO)/amorphous SiO x core–shell structures were successfully synthesized by simple thermal evaporation. Studies indicated that the core–shell structures typically consisted of a core of crystalline, ITO nanowires surrounded by a shell of amorphous, SiO x tubular structures. We proposed a gold-catalyzed, vapor–liquid–solid process as the dominant mechanism for the growth of the core ITO nanowires, whereas SiO x was grown in a tubular structure by a simultaneous and dynamic process. The possible reason for the preferential formation of the SiO x shells on the outside of the core–shell structures, is discussed. In regard to the core/shell structures, three emission peaks of 2.73, 3.06, and 1.65eV were observed in the room-temperature photoluminescence measurements, and were attributed to the SiO x shell.