context: Fluorination can be used as a strategy to suppress the anionic redox activity, which leads to irreversible oxygen gas formation. It has also been found that the fluorination increases accessible capacity when sufficiently high concentration of fluorine is added. In spite of high fluorine content, there have been some experimental observations which indicate the anionic redox activities of oxyfluorides such as Li2Mn2/3Nb1/3O2F, Li2Mn1/2Ti1/2O2F and Li2MnO2F when they are charged up to 4.5 V or above. In this work, we focus on Li2VO2F material as a comprehensive electrochemical study showed promising results such as good initial capacity and rate capability. However, it suffers from poor cycling performance due, in part, to degradation processes occurring at the electrode–electrolyte interface during extended cycling. We report a comprehensive computational and experimental investigation on the evolution of the anionic redox process in Li2VO2F under typical cycling conditions. The computational simulations suggest that the oxygen species evolve subsequently to peroxide and to superoxide when the cell is charged up to 4.1 V, a potential lower than the commonly used upper limit of 4.5 V to 4.8 V. The formation of superoxide is confirmed using electron paramagnetic resonance spectroscopy. The superoxide remains to be present in the material upon discharge, which suggests that the superoxide formation is not entirely reversible and can contribute to the capacity fading of the material upon cycling.