Among the various transition metal oxides used in lithium-ion battery anodes, iron oxide (Fe2O3) has received extensive attention due to its low cost, good environmental compatibility and high theoretical capacity. However, the volume expansion and structural collapse during the charging-discharging cycling process significantly limited the practical application of Fe2O3. Herein, we demonstrate enhanced electrochemical properties and stability of Fe2O3 by anchoring it on metal-organic frameworks (MOFs). Through adjusting the MOF ligands and introducing humic acid (HA), we reached rational control of the morphology for the Fe2O3/MOF composites. The optimized sample, namely Fe2O3@HA-Fe-ATA, shows 3D cauliflower-like structure with abundant pores, which are beneficial to the active sites exposure, electrolyte penetration, as well as the tolerance toward volume expansion. Consequently, high reversible capacity of 1442.7 mAh g−1 (at 0.1 A g−1), excellent rate performance (<11 % capacity decrease when current density increases from 0.1 A g−1 to 1 A g−1), and satisfactory cycle stability (91 % capacity retention after 500 cycles at 1 A g−1) are obtained. This work demonstrates that the rational design of MOF by introduction of appropriate ligand is a very efficient approach to optimize the electrochemical properties of the resultant electrode material.