The electronic structure of the electrochemically Li-ion deintercalated Li1−x Mn2O4 system has been investigated for various Li compositions using soft X-ray absorption spectroscopy (XAS) for oxygen K-edge and Mn LII,III-edge. To get reasonably good XAS spectra for the electrochemically Li-ion deintercalated Li1−x Mn2O4 system, we made a binder free LiMn2O4 film electrode using electrostatic spray deposition (ESD) technique. From the Mn LII,III-edge XAS, it is found that the peak shifts to higher energy with the Li-ion deintercalation and this is due to the increase of the average oxidation state of the Mn ion. From the oxygen K-edge XAS, the Li-ion deintercalation gives rise to a gradual increase in pre-edge peak intensity but mostly does not effect its peak shape.