A solid electrolyte interphase (SEI) formed on a model LiCoO2 electrode was analyzed by the ultra-soft X-ray absorption spectroscopy (XAS). The data of Li K-, B K-, C K-, O K-, and Co L-edges spectra for the SEI film on the electrode were collected using three detection methods with different probing depths. The electrode was prepared by a pulsed laser deposition method. All the spectral data consistently indicated that the SEI film containing lithium carbonate was instantly formed just after the soak of the electrode into the electrolyte solution and that it decomposed during the repeated charge–discharge reactions. The decomposition of the SEI film seems to cause the deterioration in lithium ion battery cycle performance. By adding lithium bis(oxalate) borate (LiBOB) to the electrolyte the decomposition could be suppressed leading to longer cycle life. It was found that some of the Co ions at the electrode surface were reduced to Co(II) during the charge–discharge reactions and this reaction could also be suppressed by the addition of LiBOB.