Hierarchical SnO2/Fe2O3 hollow spheres are fabricated through the solvothermal method accompanied by a facile solution procedure in the absence of any surfactant. The composition, crystalline structure, morphology, and electrochemical properties of the synthesized product are investigated systematically. The SnO2/Fe2O3 as an anode material in Li-ion batteries demonstrates a better reversible capacity and very good rate capability and cyclic performance compared with pure-phase SnO2 hollow spheres. The greatly enhanced Li-ion storage capability of the SnO2/Fe2O3 hollow spheres is believed to result from the synergy of the two materials, SnO2 and Fe2O3, which provides breathable aggregates for effective buffering of the drastic volume changes during the charge/discharge process. This work reports a promising method for the design and preparation of nanocomposite electrodes for Li-ion batteries.