In this study, a core-shell nanostructure Fe2O3 coated grass-like Mn3O4 supported on graphene has been designed and fabricated via a facile and convenient hydrothermal method and thermal treatment routes. The Fe2O3 coated Mn3O4 nanorods with diameter of 35–40 nm are convolved by flexible graphene, which form a three-dimensional conductive network. As an anode for lithium-ion batteries, the as-prepared composite delivers an initial discharge/charge capacity of 1939.2/1393.5 mAh g−1 with a promising coulombic efficiency of 71.9% and a reversible specific capacity of 795.4 mA g−1 after 400 cycles at a high current density, which exhibits an upward trend in the capacity after long-term cycling as well. Both of the cross-linked structure and the synergistic effect are contributed to the enhance lithium-storage performance and dynamic characteristic, which reveals that the electrode holds a great potential as an anode material for rechargeable Li-ion batteries.