A cryogel-forming vinyl alcohol co-polymer is operable to form a cryogel, i.e., a hydrogel formed by crytropic gelation, in an aqueous solution at a concentration of less than about 10% by weight, in the absence of a chemical cross-linking agent and in the absence of an emulsifier. In one embodiment, a vinyl alcohol co-polymer cryogel comprises at least about 75% by weight water and a vinyl alcohol co-polymer, wherein the vinyl alcohol co-polymer is operable to form a cryogel in an aqueous solution at a concentration of less than about 10% by weight, in the absence of a chemical cross-linking agent and in the absence of an emulsifier. In another embodiment, a vinyl alcohol co-polymer cryogel comprises at least about 75% by weight water and a vinyl alcohol co-polymer comprising a saponified product of a vinyl acetate co-polymer formed from at least about 80% by weight of vinyl acetate monomer, and (i) at least about 3% by weight of acrylamide monomer or a mixture of acrylamide monomer and acrylic acid monomer, or (ii) at least about 5% by weight acrylic acid monomer. The vinyl acetate co-polymer, vinyl alcohol co-polymer and vinyl alcohol co-polymer cryogel may be formed according to particular methods, and the vinyl alcohol co-polymer cryogels may be used in various applications including biomedical implants and thin films and for delivery of therapeutic or cosmetic agents.