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Anionic polysaccharide (PS) was extracted from Aphanothece stagnina biomaterials where trivalent metal ions were remarkably condensed from environmental water. Structural analyses indicated that the PS was considered to be a kind of sulfated rhamnoglucan-containing uronic acid at a composition of 23 mol% and that the total composition of anionic groups such as sulfate and carboxylate was 31 mol% to the monosaccharide residues. Since the PS was found to be a huge macromolecule with an ultra-high molecular weight (3.14 × 10 g/mol), the simple calculation indicated that about 9.5 × 10 anions exist on one chain of the PS. The electric conductivity of the highly anionic PS solutions indicated that the metal ions such as Ga, La, and Ca complexed ionically with PS chains. The PS formed the gels as a result of trivalent metal complexation, but the gelation behavior of the PS was different from that of the representative metal-complexable polysaccharide, alginate, in terms of the minimum gel formation concentration and the average molecular weight between cross-linking points. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]