Metal-organic frameworks (MOFs) are considered promising candidates for anode materials in Li-ion batteries (LIBs) owing to their designable structure, abundant active sites, and well-organized porosity. However, the structural factors governing active site utilization and Li-ion storage kinetics remain inadequately understood. In particular, the Li-ion storage behaviors of aromatic rings with high LUMO energy levels and situated in varying chemical environments remain a highly debated issue. Herein, a new cobalt-based MOF (Co-NTTA, NTTA ligand: 5,5',5''-((4,4',4''-nitrilotris (benzoyl)) tris-(azanediyl)) triisophthalic acid), featuring aromatic rings situated in diverse local environments, is deliberately designed and synthesized. Experimental characterizations and first-principles calculations have verified the occurrence of a reversible electrochemical reaction involving a total of 51 electrons among the NTTA ligands, cobalt cations, and Li