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SiOx‐modified porous biocarbon (C/SiOx), derived from shaddock peel through pyrolysis reaction, has been explored as an anode in rechargeable lithium batteries. The hierarchical structure endows the C/SiOx composites ultrahigh specific capacity and high electronic conductivity. After 100 cycles, a reversible capacity over 740 mAh⋅g−1 can be obtained at a current density of 0.358 A⋅g−1. An acceptable capacity of 82 mAh⋅g−1 can also be exhibited by withstanding a current density of 17.9 A⋅g−1. The study demonstrates that C/SiOx composites can be employed as a potential anode for advanced Li‐ion batteries.