The Pechini sol-gel method was applied to obtain LiMn2–xTxO4 (T = Ni, Fe; x = 0.1 to 0.5) nanopowders. Crystal and electronic structures, chemical composition and magnetic properties of the materials were characterized by X-ray diffraction, XPS, SEM/EDX microscopy, prompt gamma-ray activation analysis (PGAA), Mössbauer spectroscopy and magnetic susceptibility, respectively. XRD measurements showed that the LiMn2–xNixO4 were single phase for x = 0.1 and 0.2. Three samples with higher Ni content contained some addition of a second phase. Analysis of the oxidation state of the dopants by XPS revealed ionic Ni2+ and Fe3+. Mössbauer spectroscopy also confirmed 3+ oxidation state of iron and its location in octahedral sites, which excluded the inverse spinel configuration. XPS examinations showed that Mn3+ ions dominated in the iron substituted series whereas the Mn4+ was dominant in the nickel series.