High-capacity silicon (Si) is a promising material for manufacturing high-energy-density lithium-ion batteries. However, its practical applicability is severely restricted by the rapid degradation in its cycle life and calendar life. Within the context of the established understanding, Si failures are typically attributed primarily to the notable volume expansion effects of this material. However, the crucial role of chemical corrosion (e.g., hydrofluoric acid-driven corrosion) is frequently underestimated, despite its significant impact on the stability of both Si itself and the solid electrolyte interphase. In this review, the mechanisms of corrosion-induced Si degradation and the limitations of the existing mitigation strategies are systematically examined. More importantly, a novel perspective is proposed, thereby emphasizing galvanic corrosion driven by cathode oxidants, transition metal ion dissolution, and carbon additives, as well as chemical–mechanical coupling failures induced by Si corrosion. Finally, we advocate for the use of advanced characterization techniques, theoretical simulations, and holistic approaches integrating cathode design, auxiliary material optimization, and electrolyte engineering to address coupled chemical–mechanical failures for advancing the practical deployment of Si-based batteries.