Polyvinyl alcohol (PVA) hollow containers were successfully prepared through thermal processing, based on intermolecular complexation and plasticization, by adopting water and polyhydroxy compounds as composite modifiers. By high pressure capillary rheology, X- ray diffraction, dynamic mechanical properties, barrier properties and water contact angle testing methods, the melt rheological behaviors of the modified PVA system and the effects of different heat treatment conditions on the comprehensive properties of PVA hollow containers were investigated. The results show that the melt rheological behaviors of the modified system could meet the requirements of the blow molding, and the hollow containers obtained by blow molding exhibit good appearance. Heat treatment could control the water content of PVA hollow container, and adjust its crystallinity, melting point (Tm) and glass transition temperature (Tg), which improve its mechanical properties and barrier properties. After the heat treatment at 120 ℃ for 2 h, the crystallinity of the PVA hollow container increases from 22.2% to 34.7%, Tg increases from -3 ℃ to 30 ℃, the tensile strength increases from 30.4 MPa to 80.3 MPa, thepermeability to petroleum ether decreases from 2.33 g? mm/(m² ? d) to 0.73 g? mm/(m² ? d), and the water contact angle increases from 31.0° to 78.1°.