The glycerophospholipid (GPL) content and acyl group compositions of isolated brain endothelial fractions have been determined in the developing rat. During development there is a marked change in the proportions of ethanolamine glycerophospholipids (EGP) to choline glycerophospholipids (CGP), the former rising while CGP falls with age. The acyl group compositions of plasmenylethanolamine (P-GPE) and 1,2-diacyl-sn-glycero-3-phosphocholine (D-GPC) after significantly during development; both show a decline in saturated fatty acids (SFAs) and a rise in the n-6/SFA ratio, in contrast to a constancy in composition of 1,2-diacyl-sn-glycero-3-phosphoethanolamine (D-GPE). The degree of change in the acyl group composition in a particular GPL fraction is related to the rate of its accumulation and to the proportional increase in concentration, fractions accumulating most rapidly or increasing markedly in concentration showing the greatest acyl group compositional change. The possible significance of the high proportion of SFAs in P-GPE and D-GPC fractions in the developing brain endothelial fraction is discussed in relation to the altering blood-brain barrier capacities observed with age.