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Silicon-based photovoltaic technology is helpful in reducing the cost of power generation; however, it suffers from economic losses and environmental pollution caused by silicon cutting waste. Herein, a hydrothermal method accompanied by heat treatment is proposed to take full advantage of the photovoltaic silicon cutting waste and biomass excrementum bombycis to fabricate flake-like porous Si@C (FP-Si@C) composite anodes for lithium-ion batteries (LIBs). The resulting FP-Si@C composite with a meso-macroporous structure can buffer the severe volume changes and facilitate electrolyte penetration. Meanwhile, the slightly graphitic carbon with high electrical conductivity and mechanical strength tightly surrounds the Si nanoflakes, which not only contributes to the ion/electron transport but also maintains the electrode structural integrity during the repeated lithiation/delithiation process. Accordingly, the synergistic effect of the unique structure of FP-Si@C composite contributes to a high discharge specific capacity of 1322 mAh g−1 at 0.1 A g−1, superior cycle stability with a capacity retention of 70.8% after 100 cycles, and excellent rate performance with a reversible capacity of 406 mAh g−1 at 1.0 A g−1. This work provides an easy and cost-effective approach to achieving the high-value application of photovoltaic silicon cutting waste, as well as obtaining high-performance Si-based anodes for LIBs. [ABSTRACT FROM AUTHOR]