SnO2–Fe2O3 hollow spheres are fabricated with solid acid sphere as template, which presented excellent electrochemical performances with capacity of 595.5mAhg−1 at 0.2 C (160mAg−1) in the potential range of 0.05–1.2V (vs. Li+/Li), upon 50 cycles, the capacity retentions is 96.9%. Compared with SnO2 hollow spheres, SnO2–Fe2O3 hollow spheres electrode has an improved rate capability, when charged at 10 C (8000mAg−1), the capacity can reach 400mAhg−1, which is about 67% of that at 0.2 C. This excellent high rate performance of SnO2–Fe2O3 material is related to the reduction of Fe2O3 in the initial discharge process, the hollow structure and the constructing particles with nanosize, which help to improve the electronic conductivity, buffer the huge volume change and stabilize the structure.