Poly(vinyl alcohol) (PVA) films are widely used in packaging due to its excellent gas barrier, fragrance preservation, resistance to oils and chemicals, high tensile strength, transparency, printability, etc. However, due to its poor thermal processibility, PVA films available in market are usually manufactured by solution casting with complicated process, long production cycle, low production efficiency and high operating cost. Many attempts have been made to realize blow molding of PVA, which has not succeeded industrially up to now. Based on molecular complexation and plasticization, our research group has successfully realized the thermal processing of PVA by using N containing compound and water as modifier, a 500 t/a pilot production line of thermally processable PVA master batches has been set up. This paper reported the blow molding of PVA master batches and the structure and properties of PVA blown films. The experimental results showed that the melt point of PVA master batches was about 150℃ tested by DSC using a high-pressure stainless steel pan, which was far below the melting point of pure PVA of 226℃ and its thermal decomposition temperature. The melt viscosity of PVA master batch was about 150-550Pa•S at the shear rate of 100-2000s-1, which showed good flowability and was able to continuous blow molding. The tensile strength of PVA blown films was about 31MPa at 23℃, 50%RH. To further enhance the mechanical properties of PVA blown films, thermal drawing was conducted which could adjust the intermolecular interactions between modifier and PVA and increased the crystallinity, mechanical and thermal properties as well as water resistance of the films. By adjusting the drawing temperature and drawing ratio, PVA film with strength of 203MPa was obtained. Comparing with the solution casting, blow molding of PVA is an efficient and environment friendly technique, which will surely enlarge the application area of PVA films. Acknowledgements: We are grateful for the support of the National Natural Science Foundation of China (No. 50833003) and our industrial partner Sinopec Sichuan Vinylon Works of China