Nanocomposite polymer electrolytes (NCPE) composed of poly(ethylene oxide) and nanochitin for different concentrations of LiN(C2F5SO2)2 (LiBETI) were prepared by a completely dry, solvent-free procedure using a hot press. The thermal stability of NCPE membranes was investigated by DSC and TG-DTA. The membranes were subjected to SEM, ionic conductivity and FTIR analysis. Li/NCPE/Li symmetric cells were assembled and the variation of interfacial resistance as a function of time was also measured. The surface chemistry of lithium electrodes in contact with NCPE revealed the formation of Li–O–C and LiN compounds. LiFePO4/NCPE/Li cell was assembled and the cycling profile showed a well-defined and reproducible shape of the voltage curves thus indicating a good cycling behavior of the cell at 60°C.