As one of the most promising anode materials in lithium-ion batteries (LIBs), SnO2 attracts wide research attention. The practical application of SnO2 anodes, however, is mainly hampered by huge volume variation during cycling and large initial irreversible capacity. In this paper, three-dimensional porous SnO2-Fe2O3 composite films have been fabricated using the electrostatic spray deposition technique. As an anode for LIBs, the hierarchical porous SnO2-Fe2O3 film possesses a high reversible capacity (1034.1 mAh g-1) and a high initial Coulombic efficiency of 82.9% at a current density of 0.2 A g-1. At the same time, it shows good capacity retention with a capacity of 1025.6 mAh g-1 after 240 cycles and excellent rate performance. The enhanced lithium storage performance should be attributed to the synergistic effect between SnO2 and Fe2O3, as well as the three-dimensional hierarchical porous structure. The results demonstrate that such a three-dimensional porous composite anode shows great potential for application in high-energy lithium-ion batteries.