Silicon has been considered as one of the most promising anode materials for the next generation lithium-ion battery due to its high theoretical capacity, but large volume changes during the electrochemical cycling limit its commercial application. In this study, we report the synthesis of silicon carbide @ silicon core–shell nanowires on carbon paper and their application in lithium-ion batteries. The hybrid nano-structures are fabricated via a two-step chemical vapor deposition method and directly used as the working electrode without any additional binder, exhibiting high specific capacity, high coulombic efficiency and good cycling stability. After 50 cycles, the discharge capacities still remain 2837 and 1809 mAh g−1 at the rates of 0.1C and 0.5C, respectively. Furthermore, we also study the influence of the growth time of SiC NWs and the thickness of Si film on the lithium-ion batteries' performance, and propose the possible method to further improve the battery performance.