We demonstrate the in situ synthesis of carbon doped porous silicon (Si/C) nanocomposites by a simple thermal displacement process between Mg2Si and inorganic gas CO2 in one-step. Via the decomposition of Mg2Si, the reduction process occurred between Mg and CO2, leading the uniform doping of many distributed tiny carbon nanoparticles into Si. Meanwhile, the porous structure was formed after an acid treatment. When worked as anodes for lithium-ion batteries, the as-prepared s-porous Si/C nanocomposites exhibited good cycling stability and high-rate capability, which were superior to the porous Si and porous Si/C nanocomposites. It was revealed that the enhanced electrochemical properties could be ascribed to the novel porous structure and doped carbon nanoparticles that can buffer the volume expansion, as well as enhance the electronic conductivity of Si. The reaction mechanism was well investigated by studying the influence of reaction temperature and raw Mg2Si particle size on the morphology and component of the porous Si/C nanocomposites.