In this study, Fe(NO3)3.6H2O was used as the iron source for synthesising Fe2O3 and Fe2O3/C nanomaterials by microwave together with calcination. Physical characterisations of the synthesised materials have been evaluated by x-ray diffraction (XRD) and scanning electron microscopy (SEM) together with x-ray energy-dispersive spectroscopy (EDS), respectively. The Fe2O3/C composite electrodes were prepared based on Fe2O3/C nanomaterials and used as the negative electrode in the iron-based rechargeable battery. The electrochemical properties of Fe2O3/C composite electrodes were investigated by cyclic voltammetry and galvanostatic charge/discharge measurements. The obtained results show that the synthesised conditions affect the redox reactions of the Fe2O3/C electrodes. The influences of additives on the electrochemical properties of Fe2O3/C electrodes were also examined. The additives in electrode and electrolyte improved the cyclability, discharge capacity of Fe2O3/C electrode.