Ternary transition metal oxides (TTMOs) have attracted considerable attention for rechargeable batteries because of their fascinating properties. However, the unsatisfactory electrochemical performance originating from the poor intrinsic electronic conductivity and inferior structural stability impedes their practical applications. Here, the novel hierarchical porous NiO/β-NiMoO4heterostructure is fabricated, and exhibits high reversible capacity, superior rate capability, and excellent cycling stability in Li-ion batteries (LIBs), which is much better than the corresponding single-phase NiMoO4and NiO materials. The significantly enhanced electrochemical properties can be attributed to its superior structural characteristics, including the large surface area, abundant pores, fast charge transfer, and catalytic effect of the intermediate product of metallic nickel. The NiO/β-NiMoO4heterostructure delivers a high capacity of 1314mAhg-1at 0.2Ag-1after 100cycles. Furthermore, even after 400cycles at 1Ag-1, the reversible capacity remains at around 500mAhg-1. These results indicate that the NiO/β-NiMoO4heterostructure shows great potential as an anode material for high-performance LIBs.