A composite lithium battery electrode of LiMn2O4 in combination with a gel electrolyte (1 M LiBF4/24 wt% PMMA/1:1 EC:DEC) has been investigated by galvanostatic cycling experiments and electrochemical impedance spectroscopy (EIS) at various temperatures, i.e. −3<T<56°C. For analysis of EIS data, a mathematical model taking into account local kinetics and potential distribution in the liquid phase within the porous electrode structure was used. Reasonable values of the double-layer capacitance, the exchange-current density and the solid phase diffusion were found as a function of temperature. The apparent activation energy of the charge-transfer (∼65 kJ mol−1), the solid phase transfer (∼45 kJ mol−1) and of the ionic bulk and effective conductance in the gel phase (∼34 kJ mol−1), respectively, were also determined. The kinetic results related to ambient temperature were compared to those obtained in the corresponding liquid electrolyte. The incorporated PMMA was found to reduce the ionic conductivity of the free electrolyte, and it was concluded that the presence of 24 wt% PMMA does not have a significant influence on the kinetic properties of LiMn2O4.