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Controlling the morphology of metal–organic frameworks to improve their application in energy storage remains a particular challenge. In this work, hollow porous Co-MOF-74 nanocuboids consisting of nanothorn (< 7 nm) are designed through the linker exchange method for the improved MOFs-based anode of the lithium-ion battery. The Co-MOF-74 inherits the shape of cobalt acetate hydroxide prism and translates into the hollow structure due to the Kirkendall effect. The evolutions of morphology depending on temperature have been investigated further together with the lithium storage performances. Due to the combined merits from the high surface area inheriting from the nanocuboids and the coordination defects originating from the ultrasmall nanothorns, the Co-MOF-74 with optimized morphology exhibits a high reversible capacity and excellent cycle stability (up to 900 mAh g−1 at 1000 mA g−1 after 600 cycles). This work demonstrates an effective way for rational design and synthesis of MOFs-based electrodes for energy storage. [ABSTRACT FROM AUTHOR]