We describe a new type of composite skeletal tissues in which calcite and stabilized amorphous calcium carbonate (ACC) coexist in well-defined domains. The organisms that form such structures are widely separated in the animal kingdom phylogenetic tree: calcareous sponges and ascidians. This paper compares the microstructures of their composite skeletal elements: The triradiate spicules from the sponge Clathrina are composed of a core of calcite embedded in a thick layer of ACC and covered by a thin calcitic envelope; the tunic spicules from the ascidian Pyura pachydermatina are composed of a core of ACC enveloped by an insoluble organic sheath and covered by a thick calcitic layer. We compare and contrast the macromolecules associated with different amorphous and crystalline phases and their ability to induce the formation of stabilized ACC in vitro.