Spinel lithium manganese oxides LiMn1.6M0.4O4 (M=Mn, Co, Cr, Ni) for the cathode materials of the lithium ion secondary batteries were studied by electron energy loss spectroscopy (EELS). The ELNES spectra at Mn L- and O K-edge of the extracted lithium or substituted to Mn 16d site with third cations were successfully obtained. Electrochemically deintercalated Li1−x Mn2O4 showed a chemical shift of both Mn L- and O K-edges to the higher energy side compared with those of the stoichiometric LiMn2O4 indicating oxidation of Mn and O due to the electrochemical deintercalation of Li. Substitution of M for Mn (M=Co, Cr, Ni) also caused a similar spectral shift of Mn L- and O K-edges. These shifts suggest lowering of the energy levels of the inner atomic orbitals compared with that of LiMn2O4.