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This review presents and critically evaluates recent advances in non-conventional gelation method of native alginate. A special focus is given to the following three methods: cryotropic gelation, non-solvent induced phase separation and carbon dioxide induced gelation. A few other gelation approaches are also briefly reviewed. Results are discussed in the context of subsequent freeze and supercritical drying. The methods are selected so as to provide the readers with a range of novel tools and tactics of pore engineering for alginate and other anionic polysaccharides.