Bismuth oxide directly grown on nickel foam (p-Bi₂O₃/Ni) was prepared by a facile polymer-assisted solution approach and was used directly as a lithium-ion battery anode for the first time. The Bi₂O₃ particles were covered with thin carbon layers, forming network-like sheets on the surface of the Ni foam. The binder-free p-Bi₂O₃/Ni shows superior electrochemical properties with a capacity of 668 mA h g⁻¹ at a current density of 800 mA g⁻¹, which is much higher than that of commercial Bi₂O₃ powder (c-Bi₂O₃) and Bi₂O₃ powder prepared by the polymer-assisted solution method (p-Bi₂O₃). The good performance of p-Bi₂O₃/Ni can be attributed to higher volumetric utilization efficiency, better connection of active materials to the current collector, and shorter lithium ion diffusion path.