A method of preparing a metal-carbon composite of a core-shell structure through simultaneous vaporization, in which a metal particle constitutes a core and carbon constitutes a shell, with the metal-carbon composite prepared in the form of powder and supported on a supporter, and a metal-carbon composite of a core-shell structure prepared by the same. In these methods, the metal-carbon composite of the core-shell structure is prepared through simultaneous vaporization of metal and carbon precursors and does not require separate post-processing. Further, in the metal-carbon composite of the core-shell structure prepared by these methods, a carbon shell covers a portion or the entirety of a surface of a metal core, whereby the metal particles can be prevented from suffering agglomeration, separation or corrosion when subjected to harsh process conditions at high temperatures for long durations under strong acid and alkali conditions, thereby providing high performance and high durability.