Spinel LiMn2O4 was prepared by solution combustion synthesis. The effect of fuel content and calcination procedure on phase composition and microscopic structure of LiMn2O4 was studied. X-ray diffraction patterns showed that fuel content had no obvious influence on the grain size and phase purity of LiMn2O4. Higher calcination temperature led to higher phase purity, lager grain size, and better crystallization of resultant LiMn2O4. Below 600°C the effect of calcination time was inconspicuous, which became notable above 700°C. Scanning electron microscope images showed that nanocrystalline LiMn2O4 was obtained when the calcination temperature was lower than 600°C and the grain size increased at higher temperatures.