Poly(vinyl alcohol)(PVA) films play an increasingly important role in packaging field because of its environmentally friendly property, good barrier property to oxygen and oil, antistatic resistance as well as good mechanical property. However, the current applications of PVA films are based on and limited to solution casting method, because the melting point of PVA is very close to its decomposition temperature and its thermal processing is almost impossible. The thermal processing of PVA films is still a challenge worldwide. In this paper, we further developed our thermal processing technology of PVA. Together with water, environmentally friendly compounds were adopted to modify PVA, thus obtaining the thermal processing window of above 80oC. In this way, the thermal blowing films of PVA were realized, and PVA films with tensile strength of 33MPa, excellent barrier resistance in alternating environment humidity, good anti-blocking resistance were prepared. The stable melt extrusion-biaxial stretching of PVA films were also realized. With the plasticizing function of water and other compounds, the extruded sheets could be biaxially stretched to 3.5 times at a fast speed 108mm/s, reaching tensile strength 121MPa, and light transmittance 92%. Furthermore, both the thermal blowing films and the biaxial stretching films could the requirement of hygienic standard, and could be applied in packaging of food and cosmetics, electronic device as well as upscale clothes.