The composition and structure of polysaccharides from several groups of calcareous algae (including calcareous cyanobacteria), which differ in the calcification mode (extracellular, cell wall, or intracellular), are reviewed. Two families of marine algae, Corallinaceae (Rhodophyta) and Cocolithophoraceae (Prymnesiophyta = Haptophyta), are considered in detail; they exhibit the cell wall and intracellular calcification modes, respectively, and synthesize unusual polysaccharides that seem to directly participate in the calcification process.