Some of the metal ions that are required, exploited, or simply managed in biological systems are susceptible to hydrolysis and to hydrolytic precipitation in the aqueous, aerobic environment of much of biology. Organisms have evolved exquisite mechanisms for handling these metal ions, offering striking examples of biological control over inorganic coordination chemistry. This year marks the one hundredth anniversary of the discovery of remarkably high vanadium concentrations in the blood cells of the ascidian. In the ensuing years, these marine invertebrates were established as masters of the biological chemistry of very hydrolysis-prone metals, with various ascidian species accumulating high concentrations of iron, vanadium, and titanium, among others. These three metals have very different histories of biological relevance, and many questions remain about how, and ultimately why, these organisms sequester them. This Perspective addresses the aqueous coordination chemistry that organisms like ascidians must control if they are to manipulate hydrolysis-prone metal ions, and describes some of the ascidian biomolecules that have been implicated in this phenomenon. The recently available genome sequence for one ascidian species offers a glimpse into its metal-management arsenal. It offers the opportunity to map the relatively well-studied paradigm of iron management onto the genome of an organism that is intermediate in evolution between invertebrates and vertebrates. The ascidians have much to teach us about how to manage metals like iron, titanium, and vanadium and how that ability evolved.