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.