The mesoporous α-Fe2O3/CaCO3 nanoparticles have been prepared from the mixture of Fe/Ca-hydroxides and ethylene glycol via a facile solvothermal method followed by sintering at 500 °C in air atmosphere. When used as anode materials for lithium-ion batteries, the mesoporous α-Fe2O3/CaCO3 nanoparticles show great cycling stability, excellent rate capability and improved specific capacity, which can be ascribed to the strong synergistic effect of the nanocomposite, the unique mesoporous structure and the pseudocapacitive contribution.