Effects of high pressure treatment (0, 200 and 400 MPa) on water vapour barrier, microstructure, thermal, and mechanical properties of poly (lactic acid) (PLA)/Ag nanocomposite films were investigated. The migration behavior of nano-Ag from the nanocomposite films in the presence of 50% (v/v) ethanol as a food simulant was also studied. The water vapour barrier properties increased as pressure was applied to film-forming solutions. High pressure treatment enhanced the mutual effect between PLA and nanoparticles, leading to a more compact network structure in PLA/Ag nanocomposite films. Furthermore, PLA/Ag nanocomposite films treated by high pressure were significantly affected by microstructure, thermal, and mechanical properties when, compared with untreated samples. High pressure treatment at 200 to 400 MPa significantly (p < 0.05) reduced the migration of nano-Ag from the films. Overall, high pressure treatment on film-forming solutions showed potential in improving the functional properties of nanocomposite films, especially in relation to water vapour barrier properties.