Porous SnO2/graphene composite thin films are prepared as anodes for lithium ion batteries by the electrostatic spray deposition technique. Reticular-structured SnO2 is formed on both the nickel foam substrate and the surface of graphene sheets according to the scanning electron microscopy (SEM) results. Such an assembly mode of graphene and SnO2 is highly beneficial to the electrochemical performance improvement by increasing the electrical conductivity and releasing the volume change of the anode. The novel engineered anode possesses 2134.3 mA h g–1 of initial discharge capacity and good capacity retention of 551.0 mA h g–1 up to the 100th cycle at a current density of 200 mA g–1. This anode also exhibits excellent rate capability, with a reversible capacity of 507.7 mA h g–1 after 100 cycles at a current density of 800 mA g–1. The results demonstrate that such a film-type hybrid anode shows great potential for application in high-energy lithium-ion batteries.