Two stereoregular polygluconamides, one (3) of polypeptide-type and the other (16) being a polycaproamide containing four stereocenters in the main chain of the repeating unit, have been prepared from D-glucosamine and D-glucose, respectively. The new polyamides were characterized by elemental analysis, and IR, H-1- and C-13-NMR spectroscopies. The molecular weights for 3 and 16 were estimated as 25,000 and 67,000, respectively, on the basis of viscosimetric measurements. Both polyamides display high optical activity; they are highly hydrophilic and readily soluble in water as well as in a variety of organic solvents including chloroform. Polyamide 16 is highly crystalline and yields resistant films with spherulitic texture.