In this experiment, silicon/carbon (Si/C) core-shell nanowires (NWs) were synthesized using gold nanoparticles (Au NPs) coated carbon nitride nanorods (CN NRs) as a template. To begin with, the Au NPs coated CN NRs were prepared by using plasma-enhanced chemical vapor deposition assisted with hot-wire evaporation technique. Fourier transform infrared spectrum confirms the C–N bonding of the CN NRs, while X-ray diffraction pattern indicates the crystalline structure of the Au NPs and amorphous structure of the CN NRs. The Au NPs coated CN NRs were thermally annealed at temperature of 800°C in nitrogen ambient for one hour to induce the growth of Si/C core-shell NWs. The growth mechanism for the Si/C core-shell NWs is related to the nitrogen evolution and solid-liquid-solid growth process which is a result of the thermal annealing. The formation of Si/C core-shell NWs is confirmed by electron spectroscopic imaging analysis.