Neodymium substituted Li2MnO3 samples were prepared by the solid-state reaction method. The crystal and electronic structure properties of the prepared samples were investigated by x-ray based techniques. According to the analysis, it was determined that Nd atoms did not sit in to the Cr coordinations in Nd substituted samples and built up a different crystal structure. To support the analysis of the crystal structure study of the samples, electronic structure properties of the Nd substituted samples were studied via the collected data by x-ray absorption fine structure (XAFS) spectroscopy from the Mn K-edge. The results of the data analysis revealed that due to the misfit with the ionic radii and also the oxidation states, substituted neodymium atoms built up isolated crystal domains in Li8Mn5Nd18O39 cubic crystal structure. The symmetry in Mn K-edge absorption data of the sample both in parent Li2MnO3 and Nd substituted samples confirmed that Mn coordinations has not been influenced by the Nd substitution.