Microsomes isolated from liver and brain tissue were assayed to examine transitions in metabolic capability to synthesize chain elongation-desaturation products of C18:2(9,12) during the perinatal development of the pig. Microsomal synthesis of trienes, tetraenes and pentaenes was compared for fetal, neonatal and postnatal piglets. Rates of synthesis of tetraenes and pentaenes by chain elongation-desaturation of C18:2(9,12) were greatest in liver. During the later half of gestation, the capability to synthesize tetraenes increased 2-3-fold on a per mg of microsomal protein basis. Increase in the capacity to synthesize tetraenes suggests a significant transition in the activity of delta 5 desaturase during the last half of gestation. For brain, synthesis of C22:5(4,7,10,13,16) from C18:2(9,12) was greatest at term. These observations indicate that in liver and brain the capability to chain elongate-desaturate C18:2(9,12) to longer chain homologues increases significantly during early development. It is suggested that during gestation the activity of the delta 5 desaturase limits synthesis of C20 and C22 homologues of C18:2(9,12). The metabolic conversion of C20 and C22 fatty acids by chain elongation of C20:4(5,8,11,14) does not appear to limit the synthesis of very long chain homologues of linoleic acid in fetal liver or brain.