A novel method, the hydrogel foaming, is used in this work for the production of porous, polymer-based materials by processing with supercritical carbon dioxide (CO2). This method is applied to crystalline hydrophilic polymers that, practically, exhibit no phase transition (melting or glass transition) below thermal decomposition temperature and, due to their crystallinity, do not absorb CO2. Such polymers are mainly natural (semi)-crystalline polymers (e.g. chitosan, cellulose, etc.) for which the classical polymer foaming method with supercritical carbon dioxide is not applicable. The hydrogel foaming process (similar to classical polymer foaming) is applied to gelatin, chitosan, and gelatin/chitosan blend hydrogels that are physically crosslinked and may also be chemically crosslinked with glutaraldehyde vapour. After the foaming process, water is removed from the gels by mild freeze-drying leading to porous materials. Pore size control can be achieved by controlling different process parameters. Gelatin exhibits solubility in water up to high concentrations and forms thermoreversible hydrogels, rendering it a suitable choice for the investigation of the process mechanism. The mechanism of hydrogel foaming is explored on the basis of X-ray diffraction, calorimetry, rheology, sorption. Raman spectroscopy measurements and theoretical calculations with the NRHB (Non Random Hydrogen Bonding) equation-of-state model. The sorption and Raman spectroscopy measurements suggest that, besides dissolution in water (of the hydrogel), extensive CO2 sorption by the polymer also occurs. Based on these results, a critical discussion is made and a mechanism for the hydrogel foaming is proposed. (c) 2011 Elsevier Ltd. All rights reserved.