<p>Silicon (Si) is regarded as one of the most promising anode materials for next-generation lithium-ion batteries due to its exceptionally high theoretical capacity. However, its practical application remains limited by severe volume expansion and intrinsic low electrical conductivity, leading to electrode pulverization, unstable solid electrolyte interphase, and rapid capacity fading. Here, we develop a novel nano-silicon/edge-hydroxylated graphene (Si@EHG) composite synthesized via a potassium persulfate (KPS)-assisted high-energy ball milling strategy. This scalable and environmentally benign approach enables edge-selective hydroxylation of graphite without compromising its sp²-conjugated basal plane, thereby maintaining high electronic conductivity while introducing reactive –OH groups at the edges. The edge hydroxyls promote the formation of robust Si–O–C interfacial bonds with the native SiO_x layer, effectively enhancing interfacial adhesion, stabilizing the SEI, and enabling uniform lithium-ion transport. Among the composites, the Si@EHG-3% electrode exhibits the best performance, delivering a high initial discharge capacity of 3030.9 mAh·g⁻¹, 73.94% capacity retention after 100 cycles, and superior rate capability. Electrochemical impedance spectroscopy and lithium-ion diffusion coefficient analysis reveal that EHG incorporation significantly reduces charge transfer resistance and improves ion transport kinetics. This work demonstrates a rational and scalable interfacial engineering strategy based on edge-functionalized carbon materials, providing new insights for the design of high-capacity, durable silicon anodes for advanced lithium-ion batteries.</p>