ABSTRACT Searching the high rate Fe3O4-based materials for lithium ion batteries (LIBs) is still a great challenge. Here we tackle this problem by developing a facile and green method which uses the natural cotton as a biotemplate and a activity biocarbon source. By this new method, we synthesized the mesoporous biocarbon fibers adhered with Fe3O4/Fe nanoparticles (Fe3O4/Fe/MBCFs). Fe3O4/Fe/MBCFs are a highly stable anode material for high-rate LIBs due to its excellent cycling performance at higher current and fast charging feature. This anode shows a high reversible capacity of 472mAhg−1 after 500 cycles and can be rapidly charge to 100% in 28.3min. After 160 cycles at varied current densities from 1Ag−1 to 10Ag−1, it still delivered a high discharge capacity of 524.6mAhg−1 and an ultra-high coulombic efficiency close to 100%. This is attributed to the synergistic effects of several factors including the unique mesoporous hybrid construction, the graphitized biocarbon fibers and the chemical bonding between Fe3O4 and Fe nanoparticles. This work is instructive for fabrication and design of nanostructured electrodes with extraordinary properties from biomass renewable resources.