The main role of leaf venation is to supply water across the photosynthetic surface to keep stomata open and allow access to atmospheric CO2 despite evaporative demand. The optimal uniform delivery of water occurs when the distance between veins equals the depth of vein placement within the leaf away from the evaporative surface. As presented here, only angiosperms maintain this anatomical optimum across all leaf thicknesses and different habitats, including sheltered environments where this optimization need not be required. Intriguingly, basal angiosperm lineages tend to be underinvested hydraulically; uniformly high optimization is derived independently in the magnoliids, monocots and core eudicots. Gymnosperms and ferns, including available fossils, are limited by their inability to produce high vein densities. The common association of ferns with shaded humid environments may, in part, be a direct evolutionary consequence of their inability to produce hydraulically optimized leaves. Some gymnosperms do approach optimal vein placement, but only by virtue of their ability to produce thick leaves most appropriate in environments requiring water conservation. Thus, this simple anatomical metric presents an important perspective on the evolution and phylogenetic distribution of plant ecologies and further evidence that the vegetative biology of flowering plants-not just their reproductive biology-is unique.