Hierarchical porous ZnMn₂O₄ has been prepared by an initial cotton template and subsequent calcination route. The as-prepared hierarchical porous ZnMn₂O₄ composed of numerous nanoparticles well inherit the fibre-like structure of cotton, and these nanoparticles have a size of ∼20–50 nm. The N₂ adsorption–desorption test indicates this ZnMn₂O₄ has a Brunauer–Emmett–Teller surface area of ∼16.7084 m² g⁻¹ and average pore size of ∼27.0 nm. As lithium ion battery anodes, the ZnMn₂O₄ can deliver a discharge capacity of 674.9 mAh g⁻¹ after 200 cycles at current density of 200 mA g⁻¹. Even at 1000 mA g⁻¹, this ZnMn₂O₄ still shows a stable discharge capacity of 541.5 mAh g⁻¹. These promising electrochemical performances may be attributed to its unique hierarchical porous structure which helps to accelerate the ions transportation and elevate the structure stability.