Lifetimes of lithium-ion batteries are often affected by deterioration of positive electrodes. It is well-known that the deterioration of the positive electrodes can be reduced by using electrolyte additives; however, the mechanism underlying this cyclability improvement needs to be clarified. In this study, we investigate electronic structure at the electrode/electrolyte interface using in situ total-reflection fluorescence X-ray absorption spectroscopy to elucidate the mechanism underlying the cyclability improvement of a LiCoO2 electrode upon addition of vinylene carbonate (VC) to the electrolyte. The results indicate that the reduction of cobalt ions at the surface of the LiCoO2 electrode, which occurs upon soaking in the electrolyte in the absence of VC, is suppressed by the presence of the VC additive. The VC additive also suppresses irreversible change in the electronic structure of the cobalt ions at the LiCoO2 surface during successive charge/discharge processes. The effects of the VC additive can be attributed to the formation of a layer of decomposed VC molecules at the LiCoO2/electrolyte interface, which plays an important role in the suppression of the irreversibility at the LiCoO2 surface during the charge/discharge processes.