For several decades attention has been directed to natural polysaccharide gels and synthesized polymer gels. The structure-function relationships at molecular level in water of polysaccharides, κ-carrageenan, ι-carrageenan, agarose (agar), and gellan family of polysaccharides (gellan, welan, rhamsan, S-657, deacetylated rhamsan and native gellan gum), which are industrially useful polysaccharides extracted from family of red seaweeds and bacteria, in principle are discussed on the view point of rheological aspects. The polysaccharide molecules (0.1% -1.0%) play a dominant role in the center of the tetrahedral cavities occupied by water molecules (99.0% -99.9%), and the arrangement is similar to a tetrahedral structure in a gelation process. The cage and hydrophobic effect play thermal dynamically dominant role in gelation process which gives lowest entropy to electrons of sugar residues. Though the chemical structure of these polysaccharides similar each other, their rheological (gelling) characteristics are quite different. Many investigations about the gelling properties of the polysaccharides have been undertaken to elucidate the structure-function relationship, but no other researchers have established mechanism at the molecular level. There is consistency in our investigations. Thus, the rheological analysis is one of significant methods for understanding the structure-function relationship of polysaccharides in aqueous media. The discussion provides many important information not only in academic field, but also in industrial one, such as food, cosmetic, pharmaceutical, drug delivery and tissue industries, and biotechnology.