The nanocrystalline LiFe x Mn2−x O4 (x =0.2–1.0) particles were prepared by ultrasonic spray pyrolysis method using nitrate salts of ingredients at 800°C in air atmosphere. Particle properties were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy. Besides, cyclic voltammetry and galvanostatic tests were performed to investigate the effects of the iron substituent amount on electrochemical behavior. Particle characterization studies show that nanocrystalline particles have spinel structure and they are in submicron size range with spherical morphology. The lowest iron doped sample (LiFe0.2Mn1.8O4) exhibits 117mAhg−1 cumulative discharge capacity at 0.5C and 88% capacity retention for 4V plateau after 50 cycles. At higher iron concentrations, substituent tends to occupy the 8a tetrahedral sites, which prevent the lithium transport in the lattice during charge–discharge process. Increasing of the iron amount in the spinel structure causes the deterioration of the electrochemical performance.