Utilizing metal oxides as substitutes for carbon anodes is imperative in advancing LIBs. Recently, the researchers regarding to the Fe2O3 have become very popular owing to its advantages such as a high theoretical capacity (1007 mAh g−1), cost-effectiveness and sustainability. In our present studies, the Fe2O3@SCTPC (Fe2O3 nanosphere coated by carbons which are obtained by the carbonizations using the sulphonated coal tar pitches) materials are firstly and successfully fabricated by a one-step hydrothermal method using the Fe(NO3)3·9 H2O and sulphonated coal tar pitches (SCTPs). An intriguing observation is that the nanosphere Fe2O3 is encapsulated by carbons with a core-shell structure. This specific core-shell structure effectively mitigates the volume expansion of Fe2O3, and exhibits a notable enhancement in conductivity. Thanks to this unique structure, the Fe2O3@SCTPC electrode has a maximum capacity of 1106.74 mAh g−1 after 100 cycles at a current density of 0.1 A g−1 and a high reversible specific capacity of 373.5 mAh g−1 after 500 cycles at a current density of 2 A g−1, when it is used as an anode material for Li-ion battery. These results suggest that adjusting the structures of carbons is crucial to develop the potential storage capacity of the covered Fe2O3.