The structures of three of the major polar lipids (PNL1a, GL1a, and PNGL1) of Methanobacterium thermoautotrophicum were elucidated. These lipids are derivatives of dibiphytanyl diglycerol tetraether (C40 tetraether; the proposed name is caldarchaeol). PNL1a is a C40 tetraether analog of phosphatidylethanolamine (proposed name: caldarchaetidylethanolamine). GL1a was identified as beta-D-glucopyranosyl-(1-6)-beta-D-glucopyranosyl C40 tetraether (diglucosyl caldarchaeol). PNGL1 has the polar head groups of both PNL1a and GL1a; one of the free hydroxyls of this tetraether is esterified with phosphoethanolamine while the other is linked to a glucosylglucose residue with the same structure as that of GL1a (proposed name: diglucosyl caldarchaetidylethanolamine). That is, PNL1a (aminophospholipid), GL1a (glycolipid), and PNGL1 (aminophosphoglycolipid) form structurally a quartet of lipids with the bare caldarchaeol. We propose a new systematic nomenclature of archaebacterial polar lipids in the "DISCUSSION," because the alternative names are too lengthy and laboratory designations of these lipids are not at all systematic. This nomenclature starts with giving the names archaeol and caldarchaeol to dialkyl diether of glycerol or other polyol and tetraether of glycerol or other polyol and alkyl alcohols, respectively, because these lipids are specific to archaebacteria. Phospholipids with a phosphodiester bond were named as derivatives of archaetidic acid or caldarchaetidic acid (phosphomonoesters of archaeol and caldarchaeol) by analogy with phosphatidic acid.