Physiological phospholipase A2 activity levels are associated with brain white matter microstructure across adolescence. Membrane docosahexaenoic acid concentration is associated with white matter microstructure across adolescence. White matter development may involve cleavage of docosahexaenoic acid from membrane phospholipids by phospholipase A2. Docosahexaenoic acid and phospholipase A2 may be implicated in myelin-related neurodevelopmental disorders.