The structure of deuterated jarosite, KFe3(S04)2(OD)6, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times larger than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) On heating, the hydrogen bonds, 01···D-03, through which the (001) octahedral tetrahedral sheets are held together, become weakened, as reflected by increase in the D···01 distance and concomitant decrease in the 03-D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.