Abstract: The thermal expansion of iron end-member staurolite has been studied by high-temperature powder X-ray diffraction methods and by modelling with the Distance Least Squares (DLS) computer program. The X-ray approach was complicated by dehydroxylation of the staurolite. Mean linear expansion coefficients for the a, b, and c cell edges of dehydroxylated staurolite determined by the X-ray method are (× 10−6 °C−1); 20–500 °C, 8.93, 8.23, and 7.95, respectively, and 20–800 °C, 7.85, 9.43, and 9.13, respectively. Expansion coefficients of a, b, and c calculated for hydroxylated staurolite using the DLS program over the same temperature ranges are (7.86, 7.18, and 7.55 × 10−6 °C−1) and (7.87, 7.17, and 7.57 × 10−6 °C−1). The good agreement between the results from the two methods supports the use of computer modelling in estimating the thermal expansion behaviour of complex structures. The latter approach could be preferable for studying hydrated minerals.