Global resources have to be used in responsible ways to ensure the world’s future need for advanced materials. Ecologically friendly functional materials based on biopolymers can be successfully obtained from renewable resources, and the most prominent example is cellulose, the well-known most abundant polysaccharide which is usually isolated from highly available biomass (wood and wooden waste, annual plants, cotton, etc.). Many other polysaccharides originating from various natural resources (plants, insects, algae, bacteria) proved to be valuable and versatile starting biopolymers for a wide array of materials with tunable properties, able to respond to different societal demands. Polysaccharides properties vary depending on various factors (origin, harvesting, storage and transportation, strategy of further modification), but they can be processed into materials with high added value, as in the case of gels. Modern approaches have been employed to prepare (e.g., the use of ionic liquids as “green solvents”) and characterize (NMR and FTIR spectroscopy, X ray diffraction spectrometry, DSC, electronic and atomic force microscopy, optical rotation, circular dichroism, rheological investigations, computer modelling and optimization) polysaccharide gels. In the present paper, some of the most widely used polysaccharide gels will be briefly reviewed with emphasis on their structural peculiarities under various conditions.