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 mAh/g at a current density of 800 mA/g, 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.