Crystalline LiMn 2 O 4 materials were synthesized through a low temperature reflux (LTR) process. The LTR material exhibits an essential electrochemical behavior to present only one transition during the charge/discharge process and gives promises for the future application. The X-ray data hardly distinguishes either conventional high temperature (HT) or LTR material since both materials possess similar molecular structure. However, solid-state NMR results suggest substantial difference for their electronic structure. The 7 Li-NMR of HT material exhibits the isotropic peak at 529ppm and spreads for 160kHz wide indicating the interaction between the lithium nucleus and the conducting electrons around the nucleus. The LTR material presents the main isotropic peak at 217ppm but spreads for almost 400kHz wide asymmetrically implying the existence of multiple electronic environments.