To investigate the modulating effect of polysaccharide upon the mineralization of iron hydroxide, a series of simulative biomineralization experiments using dextran and chitosan as organic substrates were conducted in this paper. The results showed that iron hydroxide gel nucleated and grew in polysaccharide molecules, with the self-assemble effect of dextran or chitosan, the nanometer-sized akaganeite was formed. The shape, size and crystal structural type of iron oxyhydroxide formed from iron hydroxide gel depend on the type of polysaccharide and its concentrations.