Cobalt oxide nanostructures have been successfully grown on nickel foam by a facile polymer-assisted chemical solution method for lithium-ion battery anodes. The carbon left from the decomposition of polymers is an effective binder between the metal oxides and nickel foam. As compared to the metal oxide powder prepared in a conventional way by using polymer binder and carbon black, these one-step direct growth electrodes showed much better Li storage properties with high capacities, stable cyclability, and rate capability: Co3O4 on nickel foam gave a capacity of 900 mAh g−1 at a current density of 1 A g−1 and 600 mAh g−1 at 4 A g−1. The good performances of these electrodes could be attributed to intimate contact between the active material and nickel foam, the porosity of the current collector, and the network structure of the active materials. This general method could also be applied to other transition metal oxides.