Rechargeable lithium-ion batteries (LIBs) have been explored as competitive electrochemical power sources for various energy applications due to their high energy density. To meet to the development of high-performance electrode materials for LIBs, tin oxide (SnO2) anodes demonstrate promising prospects for their high theoretical capacities. In this paper, novel hierarchical porous reduced graphene oxide/SnO2 (rGO/SnO2) networks that consist of porous SnO2 anchored on graphene scaffold are constructed by a silica template assisted nanocasting process. The as-synthesized porous rGO/SnO2 networks of improved electrical conductivity can facilitate the electron transport and also provide sufficient active sites for redox reactions, along with accommodating the large volume changes during cycling process. As an anode material for LIBs, such porous rGO/SnO2 composite exhibits substantially enhanced cycling stability and rate capacity. In addition, the anode suggests highly stable cycling performance with the discharge capacities of 595mAhg−1 (after 300 cycles) and 394mAhg−1 (after 800 cycles) at 600mAg−1 and 1000mAg−1, respectively. The strategy indicates a promising way to fabricate advanced anode materials for LIBs.