Lithium-excess layered oxides (LLOs, Li_1+xNi_yCo_zMn_1-x-y-zO₂, > 250 mAh g^-1) have lower rate capability than conventional layered oxides, which is one of the major problems to be solved for these materials. Such phenomena are attributed to the unfavorable electrochemical reactions such as sluggish kinetics and large voltage hysteresis caused by cationic/anionic redox reaction. To enhance the rate capability of LLOs, understanding the cationic/anionic redox reaction with respect to C-rate is needed. Here, we compare the electrochemical properties at low C-rate and high C-rate of two different superstructure, specifically the local structure of Li/TM ordering (Li_1.15Mn_0.51Co_0.17Ni_0.17O₂ (Li/TM ordered arrangement) and Li_1.09Mn_0.55Ni_0.32Co_0.04O₂ (Li/TM disordered arrangement)). Through in-situ quick-scanning X-ray Absorption Spectroscopy, we reveal that local atomic configuration affects the competitive reaction of cationic/anionic redox, leading to a difference in structural reversibility and electrochemical reversibility. Our study provides insight into the reversibility at high C-rate in anion redox cathode materials and helps to develop the fast charging/discharging cathode materials.