The synthesis and electrochemical properties of a lithium manganese spinel, a LiMn2O4 film and a LiMn2O4/polyaniline (PAni)/PVDF composite film were investigated. The materials were characterized using X-ray diffraction, differential thermal analysis, scanning electron microscopy and BET surface area analysis. The intercalation/deintercalation lithium was investigated using electrochemical impedance spectroscopy, cyclic voltammetry and charge/discharge cycles. The use of PAni as an electronic conductor and electroactive material optimized the process of lithium intercalation/deintercalation in this film. The stabilized lithium extraction capacity of the LiMn2O4/PAni/PVDF composite was significantly higher than for the LiMn2O4 film (138 and 52mAhg−1, respectively).