Polycrystalline metal-organic frameworks Zn4O(1,3,5-benzenetribenzoate)2 (named as MOF-177) with different morphologies have been controlled synthesized through a solvothermal route. MOF-177 electrodes for lithium storage exhibit a relatively high irreversible capacity in the first discharge process and a much lower reversible discharge–charge capacity in the following electrochemical cycles. The performance of MOF-177 is found not impressive for application in reversible lithium storage. A preliminary reaction mechanism on the basis of transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) is proposed to understand the chemical behaviors of the electrode.