PEO16–LiClO4–ZnAl2O4 nanocomposite polymer electrolyte (NCPE) films prepared by hot-pressing method have been investigated. In order to compare with the hot-pressed NCPEs, the NCPE films have also been prepared using the conventional solution-casting method. Field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC), conductivity (σ) and interface property studies have been carried out on above two kinds of films. The results show that the NCPE film prepared by hot-pressing method has smoother surface, higher interface stability, lower crystallization and melting temperature values than that prepared by solution-casting method. An all-solid-state lithium polymer battery using the hot-pressed NCPE film as electrolyte, lithium metal and LiFePO4 as anode and cathode respectively, shows high discharge specific capacity, good rate capacity, high coulombic efficiency, and excellent cycling stability as revealed by galvanostatical charge/discharge cycling tests.