Various α-Fe2O3 nanoplates have been successfully synthesized by a solvothermal method using N-methylimidazole (N-Mim) as the main solvent, and studied as anode materials for lithium-ion batteries (LIBs). Structural characterizations reveal that the as-obtained nanoplates are composed of different submits via a particle-particle assembly way. The morphologies of assembled α-Fe2O3 nanoplates could be tailored through adjusting the concentration of FeCl3 and the reaction solvents. Moreover, electrochemical results show that the assembled α-Fe2O3 nanoplates with different subunits are demonstrated to have the variation in the cycling performance and rate capability. The as-optimized α-Fe2O3 nanoplates could exhibit a discharging capacity of 603mAh/g after 50 cycles at 100mA/g. These results suggest it is plausible to tailor the subunits of assembled structures for obtaining high-performance electrode materials.