Solid electrolyte interface (SEI) films formed on Li1-xCoO2 electrodes were observed with hard X-ray photoelectron spectroscopy (FIX-PES). This paper particularly focuses on film thickness estimation using HX-PES with theoretical calculation. The validity of the calculation was proven by experiments using model SEI films. The native film formed on a LiCoO2 composite electrode was estimated to be LiF with its thickness of 5 nm. Formation of Co (II) species on top of LiCoO2 was also indicated. Storage of the electrode at 60 degrees C brought about considerable film growth (30-40 nm) with carbonate compounds formation. SEI film changes during charging of the LiCoO2 electrode were also examined. The main component in the film was deduced to be LiF or a kind of fluorite, with its thickness decreased during charging. The SEI formation mechanisms are also elucidated. (C) 2011 Elsevier B.V. All rights reserved.