Summary: A kinetic and X-ray study of the dehydroxylation of datolite, CaBSiO4(OH), has shown that the decomposition occurs very rapidly above 700°C in air, with an activation energy for the reaction of the order of 200 kcal mole −1. The transformation is topotactic, the dehydroxylated phase being tetragonal with a 7·14 Å, c 4·82 Å, and particularly well formed even at the lowest temperatures of decomposition. Single-crystal studies have shown that two orientations of the new phase exist and that the original a of datolite becomes the unique axis of the tetragonal phase while the tetragonal a axes are oriented either parallel to or at 45° to the b and c axes of datolite. The new phase appears to be a boron-containing analogue of the melilite structure, composition Ca2SiB2O7, but is metastable. The basic sheet structure is preserved during the transformation but a reorganization of the tetrahedral layer from the 4- and 8-membered rings of datolite to the 5-membered rings of the new phase is involved, together with effective removal of protons and some silicon. The transformation can be explained in terms of an inhomogeneous reaction mechanism involving migration of calcium and boron into the new phase domains and counter-migration of silicon and protons, but with only minor readjustment of oxygens. The high activation energy of the reaction is explicable in terms either of the effort necessary to remove silicon from the domains of the new phase or of the difficulty of moving the large calcium ions through a relatively close-packed structure.