The structure of a unique polythiazole-containing cyclic peptide antibiotic, amythiamicin D, was elucidated by chemical degradations and NMR spectral analyses. Acid hydrolysis of amythiamicin D gave one mole of glycine and three new amino acids. Structures of N-acetyl-O-methyl derivatives of these new amino acids were determined by NMR and UV spectral analyses. Connectivities of these amino acids were determined by HMBC experiments.