A simple one-step and low-temperature synthesis approach has been developed to grow hierarchical NiCo2S4 ultrathin nanosheets (2–3 nm in thickness) on Ni foam. Owing to the unique nanoarchitecture, the NiCo2S4 nanosheets not only offer abundant electro-active sites for energy storage, but also have good electrical and mechanical connections to the conductive Ni foam for enhancing reaction kinetics and improving electrode integrity. When used as anodes for Li-ion batteries, the NiCo2S4 nanosheets demonstrate exceptional energy storage performance in terms of high specific capacity, excellent rate capability, and good cycling stability. The mild-solution synthesis of NiCo2S4 nanostructures and the outstanding electrochemical performance enable the novel electrodes to hold great potential for high-efficient energy storage systems.