High-energy ball milling is used to recycle Si wafers to produce Si powders for negative electrodes of Li-ion batteries. The resulting Si powder consists in micrometric Si agglomerates made of cold-welded submicrometric nanocrystalline Si particles. Silicon-based composite electrodes prepared with ball-milled Si wafer can achieve more than 900 cycles with a capacity of 1200 mAh g−1 of Si (880 mAh g−1 of electrode) and a coulombic efficiency higher than 99%. This excellent electrochemical performance lies in the use of nanostructured Si produced by ball milling, the electrode formulation in a pH 3 buffer solution with CMC as binder and the use of FEC/VC additives in the electrolyte. This work opens the way to an economically attractive recycling of Si wastes.