AbstractHierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)₂@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm⁻² or 1734 F g⁻¹ at 5 mA cm⁻²) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application.