A polypyrrole/montmorillonite-polyvinylidenedifluoride/polymethyl methacrylate (PPy/MMT-PVDF/PMMA) composite film was prepared by a solvent casting technique. The surface morphology and cross-sectional structure of the 12 wt.% PPy/MMT-PVDF/PMMA composite film exhibited porosity with high specific surface area and good adsorption capacity. The 12 wt.% PPy/MMT-PVDF/PMMA composite film shows good electrolyte uptake (241%) and electrochemical stability. The ionic conductivity of the 12 wt.% PPy/MMT-PVDF/PMMA composite film with LiPF 6 organic electrolyte reaches 2.45 × 10 −3 S cm −1 at 20 °C. The Li/LiNi 1/3 Co 1/3 Mn 1/3 O 2 cell assembled with the 12 wt.% PPy/MMT-PVDF/PMMA composite film and LiPF 6 organic electrolyte exhibits good capacity retention and cycling performance at 1 C and 60 °C. At the same time, the nucleophilic substitution reacts with the PPy/MMT-PVDF/PMMA composite film and HF from hydrolysis by trace moisture of LiPF 6 in the electrolyte solution, which can inhibit the disproportionation of Mn 3+ in the LiNi 1/3 Co 1/3 Mn 1/3 O 2 electrode material and decrease the internal resistance of the cell at high temperature. In conclusion, the PPy/MMT-PVDF/PMMA composite film can be employed in Li-ion batteries.