Direct observations of structure-electrochemical activity relationships continue to be a key challenge in secondary battery research. Li-6 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can quantitatively characterize local lithium environments on the subnanometer scale that dominates the free energy for site occupation in lithium-ion (Li-ion) intercalation materials. In the present study, we use this local probe to gain new insights into the complex electrochemical behavior of activated (0).(5Li2MnO3)-Li-6.(0).(5LiMn0)-Li-6.Ni-5(0).O-5(2), lithium- and manganese-rich transition-metal (TM) oxide intercalation electrodes. We show direct evidence of path-dependent lithium site occupation, correlated to structural reorganization of the metal oxide and the electrochemical hysteresis, during lithium insertion and extraction. We report new Li-6 resonances centered at 1600 ppm that are assigned to LiMn6-TMtet sites, specifically, a hyperfine shift related to a small fraction of re-entrant tetrahedral TMs (Mn-tet), located above or below lithium layers, coordinated to LiMn6 units. The intensity of the TM layer lithium sites correlated with tetrahedral TMs loses intensity after cycling, indicating limited reversibility of TM migrations upon cycling. These findings reveal that defect sites, even in dilute concentrations, can have a profound effect on the overall electrochemical behavior.