Archaeal glycerol dibiphytanyl glycerol tetraethers (GDGT) are some of the most unusual membrane lipids identified in nature.T hese amphiphiles are the major constituents of the membranes of numerous Archaea, some of which are extremophilic organisms.D ue to their unique structures, there has been significant interest in studying both the biophysical properties and the biosynthesis of these molecules. However,these studies have thus far been hampered by limited access to chemically pure samples.Herein, we report aconcise and stereoselective synthesis of the archaealt etraether lipid parallel GDGT-0 and the synthesis and self-assembly of derivatives bearing different polar groups.