Macroporous monolithic cryogels made from poly(vinyl alcohol) (PVA) with degree of saponification 87.7% have been prepared using a crosslinking reaction with glutaralclehyde under acidic conditions at subzero ternperatures. The porous structure of the monolithic cryogels from PVA (cryoPVA), analyzed using optical microscopy, scarinina electron microscopy, and environmental scanning electron microscopy, revealed interconnected macropores up to 150 mu m in size with a noticeable microporosity of the gel walls. Differential scanning calorimetry measurement showed that more than 90% of the water in the cryoPVA monoliths was freezable water, while the amount of polymer bound water increased with increase in the polymer concentration in the cryoPVA sample. The swelling degree of cryoPVA depended on concentration of polymer in the initial reaction mixture and degree of crosslinking. The cryoPVA monoliths were elastic and spongy-like materials that can be dried, stored in dried state, and re-swelled when required. Derivatization of hydroxyl-groups of the cryoPVA monolith allowed incorporation of required functionality. (c) 2006 Wiley Periodicals, Inc.