Poly(vinyl alcohol) (PVA) is a versatile synthetic polymer, used for the design of hydrogels, porous membranes and films. Its solubility in water, film- and hydrogel-forming capabilities, non-toxicity, crystallinity and excellent mechanical properties, chemical inertness and stability towards biological fluids, superior oxygen and gas barrier properties, good printability and availability (relatively low production cost) are the main aspects that make PVA suitable for a variety of applications, from biomedical and pharmaceutical uses to sensing devices, packaging materials or wastewater treatment. However, pure PVA materials present low stability in water, limited flexibility and poor biocompatibility and biodegradability, which restrict its use alone in various applications. PVA mixed with other synthetic polymers or biomolecules (polysaccharides, proteins, peptides, amino acids etc.), as well as with inorganic/organic compounds, generates a wide variety of materials in which PVA’s shortcomings are considerably improved, and new functionalities are obtained. Also, PVA’s chemical transformation brings new features and opens the door for new and unexpected uses. The present review is focused on recent advances in PVA-based hydrogels.