Nanocomposite of Fe₂O₃ loaded on reduced graphene oxide (rGO) was prepared using hydrothermal (h-Fe₂O₃@rGO) and solvothermal (s-Fe₂O₃@rGO) method. Moreover, rGO and Fe₂O₃ nanoparticles (NPs) were prepared using solvothermal method. X-ray diffraction (XRD), Raman spectra and scanning electron microscope (SEM) was used to characterize the prepared Fe₂O₃ NPs, rGO, h-Fe₂O₃@rGO and s-Fe₂O₃@rGO. Differential scanning calorimeter (DSC) method was used to investigate the catalytic effects of h-Fe₂O₃@rGO, s-Fe₂O₃@rGO, rGO and Fe₂O₃ NPs on the thermal decomposition of TKX-50. As a result, s-Fe₂O₃@rGO prepared by solvothermal method avoids stack of rGO and has more uniform dispersion of loaded Fe₂O₃ NPs. h-Fe₂O₃@rGO, s-Fe₂O₃@rGO and Fe₂O₃ NPs can reduce the low decomposition peak temperature by 33.9, 10.9, 25.5 ℃ and 40.7 ℃, respectively. The apparent decomposition heat of TKX-50 increases to 1747, 1924, 2096 J·g^-1 and 2983 J·g^-1 due to the addition of h-Fe₂O₃@rGO and s-Fe₂O₃@rGO. s-Fe₂O₃@rGO has better catalytic effect on thermal decomposition of TKX-50 than h-Fe₂O₃@rGO and Fe₂O₃ NPs.