Formation of nanocrystalline calcia from calcite has been studied in situ via transmission electron microscopy. The crystallographic transformation occurred via two mechanisms: the first is by distortion of the cleaved rhombohedron of calcite, formed by {104} planes in hexagonal coordinates, into a cube. This produced a microstructure of oriented, elongated nanocrystals of calcia with planar boundaries. In the second mechanism, the micrometer-sized parent calcite particles broke up into nano-sized grains as the decomposition began, leading to irregularly shaped, randomly oriented nanocrystals of calcia.