A novel, economical ball milling and heat treatment of porous silicon based anodes was introduced to boost the electrochemical performance and cycle capacity of Li-ion batteries. The resultant peanut shell-like electrodes combined multiple advantageous features, including a continuous, flexible electrically conductive carbon network, a synergistic C/SiO2 coating layer and improved interfacial contact, in a peanut shell structure with void space. The electrodes achieved an initial discharge capacity of 1909mAhg−1 with coulombic efficiency of 88.8% as well as a high reversible capacity of 1179mAhg−1 after 120cycles at 0.1C. In addition, the material was capable of reaching a capacity of 493mAhg−1 even at the high charge rate of 4C. This work gives a compelling look at a novel and large-scale production method of fabricating next generation Si/C anodes for high-performance LIBs.