Pyrolysis conditions for the production of silicon/disordered carbon (Si–DC) nanocomposites using PVA as the carbon source were optimized in this work. It was found that the optimum sintering temperature for the Si–DC nanocomposites is 800°C. In order to achieve good cell performance, a high argon gas flow rate and a slow heating rate are preferred in sample preparation. The morphology of the carbon source (PVA) affects the electrochemical performance of the Si–DC nanocomposites as well. The key point to obtain Si–DC nanocomposites with good electrochemical performance is to reduce the chances of pyrolysis gases (especially CO2) to react with carbon, thereby preventing carbon burnoff during the sintering process.