LiMn2O4 powders have been directly prepared by flame spray pyrolysis from an aqueous spray solution of the metal salts. The powders prepared at a low fuel gas flow rate (3Lmin−1) comprise particles with a bimodal size distribution, i.e., submicron- and nanometer-sized particles, and have crystal structures of LiMn2O4 and Mn3O4 phases. However, the powders prepared at a high fuel gas flow rate (5Lmin−1) comprise nanometer-sized particles and have pure crystal structure of LiMn2O4 phase. The powders comprising nanosized particles are well crystallized, and the particles have a polyhedral structure. The mean particle size of these powders is 27nm. The powders prepared directly by flame spray pyrolysis comprise nanosized particles and have the pure crystal structure of LiMn2O4, irrespective of the amount of excess lithium in the precursor solution. The initial discharge capacities of these powders increase from 91 to 112mAhg−1 when the amount of excess lithium is increased from 0% to 30% of the stoichiometric amount. The optimum amount of excess lithium required to prepare LiMn2O4 powders with nanosized particles and the maximum possible initial discharge capacity is 10%.