Renewable biomass-derived monomers present a viable solution. On the other hand, conventional solvothermal methods, which involve elevated temperatures and negative pressures in sealed tubes, are the primary means of COF preparation. These methods lead to high energy consumption, complex operations, and are unsuitable for mass production. Therefore, to achieve green mass production of COFs, scientists are actively pursuing the synthesis of COFs using renewable monomers through simpler processes under mild temperature and pressure conditions. This study synthesized a novel COF, COF@bio, from biomass-derived monomers under mild conditions using a facile process. To our knowledge, this is the first report of a biomass-based COF designed and synthesized under mild conditions through the facile prepared process. The chemical structure of COF@bio, which includes benzene rings, imine linkages, and furan rings, was rationally designed to facilitate lithium storage. Additionally, to enhance conductivity and improve the active site utilization ratio, COF@bio was in situ grown on CNT to form COF@bio-40. COF@bio-40 exhibited superior capacity and improved rate performance compared to other prepared anodes and commercial graphite anodes, achieving a maximum capacity of 804 mAh g⁻¹ during long-term cycling tests and a high capacity of 364 mAh g⁻¹ at a current density of 2,000 mA g⁻¹ over 500 cycles. As confirmed by EIS and BET experiments, the COF@bio-40 demonstrated higher lithium storage capacity than the pristine COF, attributed to improved electronic conductivity and dispersed active sites. Moreover, ex-situ XPS, DFT, and capacity contribution analyses were employed to elucidate the lithium storage mechanism. The results revealed that the lithiation and delithiation processes of the COF monomer involve 11-electron redox chemistry, with one lithium ion per benzene ring, one lithium ion per oxygen, and one lithium ion per imine linkage. This work may pave the way for developing biomass-based sustainable organic electrodes with high performance for organic rechargeable batteries.