Abstract Due to their special chemical structure, tetraether lipids (TEL) represent essential elements of archaeal membranes, providing these organisms with extraordinary properties. Here we describe the characterization of a newly isolated structural element of the main lipids. The TEL fragment GDNT‐β‐Glu was isolated from Sulfolobus metallicus and characterized in terms of its chemical structure by NMR‐ and MS‐investigations. The obtained data are dissimilar to analogically derived established structures – in essence, the binding relationships in the polar head group are re‐determined and verified. With this work, we provide an important contribution to the structure elucidation of intact TEL also contained in other Sulfolobus strains such as Solfulobus acidocaldarius and Sulfolobus solfataricus.