Rational design and efficient synthesis method for electrode materials with improved functional morphologies are highly sought after in the development of rechargeable batteries. Herein, hierarchical fern leaf-like nanocomposites of alpha-Fe2O3@C connected by reduced graphene oxide (rGO), to form alpha-Fe2O3@C/rGO, have been prepared through a one-pot self-templated solvothermal method from ferrocene. A reasonable self-assembly process of the unique nanostructure is also proposed. During the in-situ formation, rGO content has a direct impact on the size of the fern leaf-like architectures, and also improves the electronic conductivity between adjacent fern leaf-like architectures. When used as anode materials for lithium-ion.batteries, alpha-Fe2O3@C/rGO nanocomposite exhibits excellent cycling performance at 200 mA g(-1), maintaining a discharge capacity of 971 mAh g(-1), after 100 cycles. Furthermore, when used as anode materials for sodium-ion batteries, it exhibits an encouragingly high reversible capacity of 720 mAh g(-1) at 50 mA g(-1) during the 2nd cycle. These results suggest the unique nanocomposite structure holds great promise for energy storage applications. (C) 2017 Elsevier B.V. All rights reserved.