A single-step solid-state synthetic approach was developed for the synthesis of silicon-coated carbon nanotube (CNT) core/shell structures. This was achieved through laser-induced melting and evaporation of CNT-deposited Si substrates using a continuous wavelength CO2 laser. The synthesis location of the CNT/Si structures was defined by the laser-irradiated spots. The thickness of the coating was controlled by tuning the laser power and synthesis time during the coating process. This laser-based synthetic technique provides a convenient approach for solid-state, controllable, gas-free, simple and cost-effective fabrication of CNT/Si core/shell structures.