Lithium manganese oxide (LiMn2O4) powder with spinel structure has been synthesized by a sol-gel method using an aqueous solution of metal nitrates containing polyvinyl alcohol (PVA). The role of PVA and the calcination conditions for the formation of LiMn2O4 have been studied. Homogeneity and reactivity of the precursor powder are enhanced with an increase in the amount of PVA in the starting solution. When the amount of PVA is low, an impurity phase-Mn2O3 is formed at low temperature. On the other hand, when the vinyl alcohol monomer unit of PVA to metal ion ratio is 2 : 1 in the starting solution, only spinel phase is formed at 180°C and organic-free LiMn2O4 powder is obtained at as low as 400°C. Nanosized LiMn2O4 particles with a narrow size distribution have been successfully prepared by this technique. This method with proper amount of PVA results in much lower calcination temperature and shorter calcination time for producing the single spinel phase in comparison with the conventional solid state reaction and other solution techniques.