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Polyvinyl alcohol (PVOH) is a synthetic hydrophilic linear polymer that generally exists as a copolymer of vinyl alcohol and vinyl acetate. Therefore, the structural properties of PVOH polymers primarily depend on the degree of polymerization and the degree of hydrolysis, ie, the ratio of the two monomers. Due to reactive functional groups on its structure, PVOH undergoes chemical changes such as esterification and etherification, as well as physical changes such as crystallization and ion-polymer complexation. Both chemically and physically-modified PVOH structures have found applications in biomedical and pharmaceutical area. This article reviews the properties of PVOH in solid and solution states, PVOH hydrogels and cryogels, their biomedical and pharmaceutical applications, and their potential challenges.