Tin–manganese oxide film with three-dimensional (3D) reticular structure has been prepared by electrostatic spray deposition (ESD). X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that the film is amorphous. X-ray-photoemission spectroscopy (XPS) demonstrates that the 3D grid is composed of tin–manganese oxide. As an anode electrode for the lithium ion battery, the tin–manganese oxide film has 1188.3mAhg−1 of initial discharge capacity and very good capacity retention of 656.2mAhg−1 up to the 30th cycle. Such a composite film can be used as an anode for lithium ion batteries with higher energy densities.