A comparative study of the impedance response measured with composite electrodes and thin film electrodes of LiMn2O4 was conducted. The electrodes were prepared on different current collectors (i.e. aluminium, carbonised aluminium and gold) and the experiments were run at various state-of-discharge (SOD) and liquid electrolyte compositions. The impedance response was shown to be strongly dependent on the current collector used. It was demonstrated that the high-to-medium frequency semicircle can be attributed to the contact resistance between the current collector and the active electrode material and that the medium-to-low frequency semicircle can be ascribed to the active electrode material. For the analysis, a mathematical model based on a resistance between the current collector and the active electrode material, interfacial-charge transfer coupled to the double-layer charging and solid-phase diffusion was developed. Potential distribution due to porous electrode effects was also considered. Fitting the model to experimental data enabled reasonable values of the exchange-current density, the double-layer capacitance and the solid-phase diffusion coefficient. However, the very low fitted value of the effective conductivity in the liquid phase indicates that this model does not give a satisfying description of the intercalation process of LiMn2O4.