Validamycin A (VM-A), isolated from the culture of Streptomyces hygroscopicus subsp. limoneus, is widely used for the treatment of sheath blight of rice plants and soil-borne plant diseases caused by Bacidiomycetes. The culture broth contains many minor components of the validamycin group in addition to VM-A, the main component. Since we published the partial structures of the minor components, such as validamycins B (VM-B), C (VM-C), D (VM-D), E (VM-E) and F (VM-F),1~3) structural analysis techniques for complicated oligosaccharides using NMR spectroscopy have developed quite remarkably. The structure of validamycin G (VM-G),43 the most recently discovered congener was established by making use of these techniques. We have now used NMR to reinvestigated the position of the glycosidic linkage of the minor components which had remained obscure. The results were first disclosed in a patent application,53 though without experimental data. Here we discussed the structures of the minor components with experimental results. To elucidate the unidentified positions of the glucosidic linkage by ¹H NMR spectroscopy, VM-B~ F were acetylated with acetic anhydride and pyridine to give the corresponding peracetyl derivatives. The chemical shifts of 1-H and l'-H of the peracetates, recognized in the region of 3.2~3.6 ppm, indicate that the imino group is not acetylated.