We report the spontaneous transformation of highly hydrated crystalline ikaite into less hydrated amorphous calcium carbonate (ACC), which has the outer contours of micrometer-sized crystals, a multi-level interconnected porous structure and a very high specific surface area (98.3 cm2 g−1). The ikaite was previously obtained by transformation of an uncommon hydrated ACC with as much H2O as ikaite, synthesized at 2 °C without any additives. The solid-state amorphization was induced by the fast dehydration of the crystal.