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This work reviews the synthesis of polyvinyl alcohol (PVA) hydrogels, methods to enhance their mechanical properties, types of bio?additives incorporated for biocompatibility, their mechanism of interaction with PVA and future prospects of PVA composite bio?hydrogels for application in various fields.Vinyl polymers are widely used in biological, textile and industrial applications and are currently attracting research attention for specialized bio?based applications. Polyvinyl alcohol (PVA) hydrogels show great advantages as a material with high biocompatibility, permeability, hydrophilicity, and low?friction coefficient, allowing applications as smart materials, wound dressings, and flexible sensors. However, the poor mechanical properties of PVA hydrogels and biocompatibility less than natural polymers make them unsuitable in practical applications. Additives are often added to PVA hydrogels to enhance mechanical properties, endow more compatibility, functionality and expand their application range. Among them, bio?additives such as nanocellulose, natural polysaccharides and proteins are biodegradable, biocompatible, and inexpensive, broadening their applications in the biomedical and tissue engineering fields. This work reviews the synthesis of PVA hydrogels, methods to enhance their mechanical properties, types of bio?additives incorporated for biocompatibility, their mechanism of interaction with PVA and future prospects of PVA composite bio?hydrogels for application in various fields. Representative cases are carefully selected and discussed with regard to their composition and pros and cons are discussed. Finally, future requirements, as well as the opportunities and challenges of these bio?additives for improving the multifunctionality of PVA hydrogels are also presented.