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Si-based anodes for Li-ion batteries (LIBs) are considered to be an attractive alternative to graphite due to their higher capacity, but they have low electrical conductivity and degrade mechanically during cycling. In the current study, we report on a mass-producible porous Si-CoSi2-C composite as a high-capacity anode material for LIBs. The composite was synthesized with two-step milling followed by a simple chemical etching process. The material conversion and porous structure were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and electron microscopy. The electrochemical test results demonstrated that the Si-CoSi2-C composite electrode exhibits greatly improved cycle and rate performance compared with conventional Si-C composite electrodes. These results can be ascribed to the role of CoSi2 and inside pores. The CoSi2 synthesized in situ during high-energy mechanical milling can be well attached to the Si; its conductive phase can increase electrical connection with the carbon matrix and the Cu current collectors; and it can accommodate Si volume changes during cycling. The proposed synthesis strategy can provide a facile and cost-effective method to produce Si-based materials for commercial LIB anodes.