The microstructure, thermal properties, mechanical properties and oxygen and water vapor barrier properties of a poly(lactic acid) (PLA)/nano-TiO2 composite film before and after high pressure treatment were studied. Structural analysis showed that the functional group structure of the high pressure treated composite film did not change. It was found that the high pressure treatment did not form new chemical bonds between the nanoparticles and the PLA. The micro-section of the composite film after high pressure treatment became very rough, and the structure was depressed. Through the analysis of thermal and mechanical properties, high pressure treatment can not only increase the strength and stiffness of the composite film, but also increase the crystallinity of the composite film. Through the analysis of barrier properties, it is found that the barrier properties of composite films after high pressure treatment were been improved by the applied high pressure treatment.