Poly(vinyl alcohol) (PVA) is an important polymer material that can be prepared in large industrial scale from coal and natural gas and has been developed very fast in recent years. However, the melting point of PVA is very close to its decomposition temperature, resulting in the difficulty in thermal processing of PVA. The current applications of PVA are based on and limited to wet process, only used as low-dimensional products such as fibers, films, or as assistants, and auxiliary materials, which seriously hinders the further development of PVA industry. This paper briefly reviewed our research work on the novel thermal processing technology of PVA and PVA based composites. Based on intermolecular complexation and plasticization, the thermal processing window of more than 120 ℃ for PVA was obtained. In this way, the melt spinning, thermal blowing, extrusion, injection and micro-injection molding as well as thermal foaming of PVA were successfully realized. Furthermore, the PVA based composites with excellent comprehensive properties such as PVA/inorganic filler and PVA/biomass material composites were obtained combining the thermal processing of PVA and solid state shear milling (S3M) technology, which will open a new application field for PVA and provide a technical and theoretical support for PVA industry.