In summary, a proof-of-concept COF@bio was constructed from two biomass-derived monomers under mild conditions and through a simple synthesis process, aligning with green, sustainable development goals and demonstrating the potential for mass production. However, due to its limited conductivity, COF@bio was in-situ growth with CNT to synthesize the composites. Among these, COF@bio-40 exhibited exceptional long-cycle stability (364 mAh g⁻¹ at 2,000 mA g⁻¹ after 500 cycles) and rate performance (approximately 660 mAh g⁻¹ at 2,000 mA g⁻¹) in LIBs under high current density, achieving sophisticated lithium storage performance compared to other prepared anodes and commercial graphite anodes. COF@bio-40 displayed remarkable stability during long-term cycling tests, with a maximum specific capacity reaching 804 mAh g⁻¹ (at 2,000 mA g⁻¹) due to the gradual activation of electrode materials. After 500 cycles, the capacity contribution from COF@bio in the COF@bio-40 composite was around 537 mAh g⁻¹. Based on the capacity contribution, XPS, and DFT analyses, the benzene rings, imine linkage, and furan rings were involved in the lithium storage process, suggesting an 11-lithium storage capacity for a single COF monomer. Thus, a high-performance COF@bio-based anode was developed from biomassderived monomers using a straightforward synthesis at room temperature, offering a promising green solution for future eco-friendly and sustainable energy-storage devices.