We fabricated ZnS/diamond-like carbon (DLC) core-shell heterostructure nanowire using a simple two-step process: the vapor-liquid-solid method combined with radio frequency plasma enhanced chemical vapor deposition (rf PECVD). As a core nanowire, ZnS nanowires with face-centered cubic structure were synthesized with a sputtered Au thin film, which exhibit a length and a diameter of ~10 μm and ~30–120 nm . After rf PECVD for DLC coating, The length and width of the dense ZnS/DLC core-shell nanowires were a range of ~10 μm  and 50–150 nm , respectively. In addition, ZnS/DLC core-shell nanowires were characterized with scanning transmission electron microscopy. From the results, the products have flat and uniform DLC coating layer on ZnS nanowire in spite of high residual stress induced by the high sp3 fraction. To further understanding of the DLC coating layer, Raman spectroscopy was employed with ZnS/DLC core-shell nanowires, which reveals two Raman bands at 1550 cm−1 (G peak) and 1330 cm−1 (D peak). Finally, we investigated the optical properties from ultraviolet to infrared wavelength region using ultraviolet-visible (UV-Vis) and Fourier transform infrared (FT-IR) spectrometry. Related to optical properties, ZnS/DLC core-shell nanowires exhibit relatively lower absorbance and higher IR transmittance than that of ZnS nanowires.