Valiolamine, a new aminocyclitol has been isolated from the fermentation broth of Streptomyces hygroscopicus subsp. limoneus and its structure has been determined to be (1(OH),2,4,5/1,3)-5-amino-1-C-(hydroxymethyl)-1,2,3,4-cyclohexanetetr ol. Valiolamine has more potent alpha-glucosidase inhibitory activity against porcine intestinal sucrase, maltase and isomaltase than valienamine, validamine and hydroxyvalidamine which were reported as building blocks of validamycins and microbial oligosaccharide alpha-glucosidase inhibitors. In addition, valienamine, validamine and hydroxyvalidamine have been isolated from the fermentation broth.