The modification of electrochemistry and electronic absorption spectra of neodymium in various molten chlorides depending on additional fluoride in the melt bath has been investigated. Disproportionation reaction is restricted by fluoride addtion and absorption spectra is highly modified in molten NaCl-2CsCl as compared with that in molten LiCl-KCl. These facts would be explained by modification of local structure around neodymium cation depending on fluoride addition.