In this work, a binder-free, self-supported, three-dimensional (3D), porous Li3VO4 (LVO) and the carbon-coated Li3VO4(LVO@C) anode materials are prepared on a Ni-foam disc by the electrostatic spray deposition technique. The deposited materials exhibit a unique morphology with sponge-like 3D porous hierarchical architecture. The novel structure can significantly enhance the surface area of the materials, relax the stress/strain of Li+ insertion/deinsertion, and obviously shorten the diffusion path of lithium ions in the charger/discharge process. The porous nickel-foam substrate can also provide an electric transport network and structural support to the electrode, resulting in very excellent rating and cycling performance. In addition, the coated carbon network can further facilitate the electric transport of the material. As a result, both electrodes show outstanding electrochemical properties, especially the LVO@C electrode. The discharge capacities of LVO@C are 508.8, 424.1, 405, 377.5, and 340.1 mA h g–1 at 0.5, 5, 10, 20, and 30 C, respectively, and the capacity can persist at 399 mA h g–1 without any capacity fading even after 1000 cycles at the current density of 10 C. The excellent properties make these LVO-based materials, especially the carbon-coated LVO composite, a promising anode candidate for the low-cost and high-performance LIBs.