The behavior of hydrated zirconium fluoride has been studied by perturbed angular correlation spectroscopy. It is found that the crystalline compound ZrF4 center dot HF center dot 2H(2)O, formed initially by drying solution of Zr metal in concentrated HF, transforms spontaneously to ZrF4 center dot 3H(2)O. This trihydrated compound dehydrates to ZrF4 through the intermediate monohydrates ZrF4 center dot H2O and Zr2OF6 center dot H2O. The compound ZrF4 finally transforms to ZrO2 at similar to 343 K. Different crystalline phases of ZrF4 center dot HF center dot 2H(2)O, ZrF4 center dot 3H(2)O, ZrF4 center dot H2O, Zr2OF6 center dot H2O, ZrF4 and ZrO2 have been identified and characterized by PAC spectroscopy. From previous PAC measurements, the intermediate ZrF4 center dot H2O and Zr2OF6 center dot H2O were not observed and the dehydration from ZrF4 center dot 3H(2)O to ZrF4 was found to be routed directly. Present measurements by PAC exhibits dissimilar crystal structures for ZrF4 center dot 3H(2)O and ZrF4 center dot H2O unlike the crystal structures found in hafnium analogous compounds. (C) 2014 Elsevier B.V. All rights reserved.