The structure of deuterated jarosite, KFe{sub 3}(SO{sub 4}){sub 2}(OD){sub 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 {approx}10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH){sub 6}] octahedra and [SO{sub 4}] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, a = a{sub 0} + a{sub 1} T, where a{sub 0} = 1.01 x 10{sup -4} K{sup -1} and a{sub 1} = -1.15 x 10{sup -7} K{sup -2}. On heating, the hydrogen bonds, O1{hor_ellipsis}D-O3, through which the (001) octahedral-tetrahedral sheets are held together, become weakened, as reflected by an increase in the D{hor_ellipsis}O1 distance and a concomitant decrease in the O3-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.