Recently, Fe2O3 has been considered as an alternative anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity (approximately 1000 mA h g–1), low cost, and nontoxicity. However, its rate performance remains poor relative to that of the conventional graphite anode. In this study, Fe2O3-based anodes were prepared through the annealing of biogenous Fe2O3 (L-BIOX) samples produced by an aquatic Fe-oxidizing bacterium. The effect of the annealing temperature on the performance of the synthesized Fe2O3-based material as the anode of an LIB was investigated. Electrochemical measurements revealed that the annealed L-BIOX samples at 300–700 °C exhibited higher rate performances than the unannealed material. Particularly, the sample annealed at 700 °C exhibited the highest capacity among the synthesized materials and showed a higher performance than the previously reported Fe2O3-based anodes. It exhibited a capacity of 923 mA h g–1 even at a high current density of 2 A g–1. After annealing at 700 °C and discharging, the synthesized biogenous material had a uniform nanocomposite structure composed of α-Fe2O3 nanoparticles dispersed in an amorphous matrix of Li–Si–P oxide. To form this uniform nanostructure, the solid-state diffusion resistance of the Li+ ions in the active material was reduced, which consequently improved the rate performance of the electrode. Therefore, this study provides substantial insights into the development and improvement of the performance of novel Fe2O3-based nanomaterials as the anode of LIBs.