The capacity of poly(vinyl alcohol) (PVA) to crosslink through freeze/thaw method was used to obtain PVA hydrogel membranes (HG) that were subjected to sorption and diffusion experiments using three dyes: Congo red (CR), methylthymol blue (MTB), and crystal violet (CV). To study the sorption of dyes into the cryogenic membrane, dye solutions at different concentrations were used. After sorption, desorption of dyes from the PVA membrane was monitored to quantify the possible regeneration of the membrane (PVA HG). To have a deep insight on the mechanism behind the desorption process, dye-release kinetics were studied. The diffusion experiments reveal the fact that CR and MTB do not permeate the PVA HG membrane making it a promising candidate in the advanced purification processes of waste-waters. The effect of the incorporation of dyes (CV, CR, and MTB) on the chemical properties of PVA cryogel matrices has been studied by using several techniques such as: differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1445-1453, 2010