The miniaturization of rechargeable lithium-ion batteries requires high quality thin-film electrodes. Electrostatic spray deposition (ESD) technique was used to fabricate LiMn2O4 thin-film electrodes with three different morphologies: sponge-like porous, fractal-like porous, and dense structures. X-ray diffraction (XRD) and scanning electron microscopy were used to analyze the structures of the electrodes. These electrodes were made into coin cells against metallic lithium for electrochemical characterization. Galvanostatic cycling of the cells revealed different rate capability for the cells with LiMn2O4 electrodes of different morphologies. It is found that the cells with LiMn2O4 electrodes of porous, especially the sponge-like porous, morphology better rate capability than those with dense LiMn2O4 electrodes. Electrochemical impedance spectroscopy (EIS) study indicates that the large surface area of the porous electrodes should be attributed to the smaller interfacial resistance and better rate capability.