The synthesis of layered double hydroxide (LDH) as electroactive material has been well reported; however, fabricating an LDH electrode with excellent electrochemical performance at high current density remains a challenge. In this paper, we report a 3D hierarchical porous flower-like NiAl-LDH grown on nickel foam (NF) through a liquid-phase deposition method as a high-performance binder-free electrode for energy storage. With large ion-accessible surface area as well as efficient electron and ion transport pathways, the prepared LDH-NF electrode achieves high specific capacity (1250 C g⁻¹ at 2 A g⁻¹ and 401 C g⁻¹ at 50 A g⁻¹) after 5000 cycles of activation at 20 A g⁻¹ and high cycling stability (76.7% retention after another 5000 cycles at 50 A g⁻¹), which is higher than those of most previously reported NiAl-LDH-based materials. Moreover, a hybrid supercapacitor with LDH-NF as the positive electrode and porous graphene nanosheet coated on NF (GNS-NF) as the negative electrode, delivers high energy density (30.2 Wh kg⁻¹ at a power density of 800 W kg⁻¹) and long cycle life, which outperforms the other devices reported in the literature. This study shows that the prepared LDH-NF electrode offers great potential in energy storage device applications.