A new cyclic depsipeptide stereocalpin A (1) has been isolated from the MeOH extract of the Antarctic lichen Stereocaulon alpinum by various chromatographic methods. The structure of stereocalpin A (1) was mainly determined by analysis of the NMR spectroscopic data and by chemical methods. Stereocalpin A (1) is a unique cyclic peptide incorporating an unprecedented 5-hydroxy-2,4-dimethyl-3-oxo-octanoic acid in the structure. Stereocalpin A (1) shows moderate cytotoxicity against three human solid tumor cell lines.