Firstly, we put forth a potentially prebiotic synthesis of choline by biomimetic stepwise methylation of ethanolamine. Secondly, embracing a systems chemistry approach, we show that ring-opening of the intrinsically activated glycerol-2,3-cyclic phosphate with combinations of prebiotic amino alcohols leads to a diverse array of phospholipid headgroups. The reactivity of biologically relevant 2-amino alcohols dictates their selection in the ring-opening reaction. Furthermore, our investigations suggest that the greater hydrolytic stability of the natural G3PXs compared to the non-natural G2PXs may have resulted in their accumulation in the prebiotic milieu. Taken together, our results offer a plausible explanation for the predominance of 2-amino alcohol-bearing G3PXs in biology. Thirdly, we demonstrate that dry-state ring-opening of 10:0 lyso G>P with amino alcohols results in the formation of a variety of complex lysophospholipids (precursors to diacyl phospholipids), which integrate into pre-existing supramolecular assemblies.