It is crucial to design and construct highly sensitive electrode materials for the detection of biomolecules. In this paper, 3D hierarchical NiMoS4 NWAs@GF was designed for the detection of epinephrine (EP). The 3D GF has a pore size of 200 μm as a conducting matrix with remarkable electronic conductivity. The grass-like NiMoS4 NWAs on the GF have a length of about 20 μm and the diameter about 180 nm, which not only increase the specific surface area but also provide more active sites. As expected, the NiMoS4 NWAs@GF/ITO electrode showed a remarkable electrochemical performance in the detection of EP in a wide concentration range (0-60 µM), with a high sensitivity of 3.93 µA µM−1, and a low detection limit of 0.02 µM (S/N=3). In addition, it can be used to determine EP in real samples. The NiMoS4 NWAs@GF/ITO electrode is proven to be a reliable and sensitive biosensor electrode.