Electrochemical behavior of LixMn2O4 powders, prepared using different synthesis approaches, have been studied using LixC6/LixMn2O4 cells based on glass-polymer composite electrolytes. Results indicate that the LixMn2O4 powders prepared by a xerogel technique have much smaller particle size, larger capacity utilization and less capacity fading during cycling in comparison to the powders prepared by solid state reactions. The electrochemical behavior of a composite positive electrode based on LixMn2O4 is influenced not only by the microstructure of the LixMn2O4 powders but also by the volume fractions of other constituent phases.