Summary: Motukoreaite resembles hydrotalcite and has positively charged brucite-like layers separated by carbonate and sulphate anions and water molecules. Four phases are recognized. Phase I, the normal mineral with an 11.1 Å basal spacing, readily changes to a mixture of phase I and a partially dehydrated phase II. Phase III with a basal spacing 8.7 Å persists from 50–170°C. Phase II is a pseudo-regular interstratification of phases I and III, with a spacing 11.1 + 8.7 = 19.8 Å; second- and third-order reflections are observed. Phase IV with a 7.5 Å spacing is obtained by treating motukoreaite with sodium carbonate solution to replace SO4 by CO3 anions. Motukoreaite itself shows only slight tendency to transform to a 7.5 Å phase by heat-treatment alone. Comparison is made with the mineral carrboydite, a NiAl sulphate carbonate hydrate. The possibility is considered that sulphate anions may substitute partially in the brucite-like layers to compensate for a deficiency of hydroxyl ions.