Transition metal oxide hollow architectures are intensively explored for energy conversion and storage applications. Feasible strategies towards various hollow architectures, particularly those with non-spherical skeletons, are especially attractive. Quadrate Co₃O₄ nanoboxes are fabricated through controlled annealing of cobalt coordination polymer nano-solids with tunable dimensions. The cobalt coordination polymer in quadrate wires, cuboids, and cubes is synthesized by temperature and concentration dependent solvothermal method. Evolution of the nanoboxes involves Co₃O₄ shell formation and uniform depletion of the cobalt coordination polymer in the core. Benefitting from the well-defined hollow interior and nanosized crystals, the quadrate nanoboxes have large specific surface and abundant hierarchical pores. When evaluated as anode materials for lithium ion batteries, the boxes exhibited excellent electrochemical properties. Besides a superior storage capability of 1200 mA h g⁻¹ at 0.2 A g⁻¹, a remarkable retention of 625 mA h g⁻¹ at a large rate of 10 A g⁻¹ is also obtained.