We have studied the lithium insertion into LiM2O4 (M = Mn, Fe, Co) using n-BuLi and electrochemical techniques. The oxides crystallized in the pure spinel phase S.G. Oh7(Fd3m). Probable cationic distributions were proposed based on XRD, Mössbauer and pzc measurements. The results demonstrate that an important factor in the extent of the lithium insertion reaction in mixed oxides is the presence of the highest oxidation state in the transition metal cations that are located in B-sites of the spinel framework