Spent limestone samples from the bed and baghouse of a 22 MWe circulating fluidized bed (CFB) boiler were hydrated and then sulphated in a thermogravimetric analyzer under conditions similar to those found in CFB combustors (850°C, 0.3% SO2, 9% O2, 9% CO2 and 81.7% N2). Hydration using water gave faster rates and higher levels of conversion of the residual CaO to Ca (OH)2 than immersion in pure steam at 150 and 200°C. The particles expanded during hydration and their internal volume increased from 0.1 cm3/g Ca before hydration to nearly 0.6 cm3/g Ca after dehydration. Hydration rejuvenated the reactivity of the bed material but not that of the baghouse particles. The conversion of Ca to CaSO4, in the treated bed particles increased from 32% to over 80% during re‐sulphation.