Elpidite Na2ZrSi6O15•3H2O is a natural zirconosilicate with space group Pbcm. A sample from Mt. Saint Hilaire (Canada) was investigated between 25 and 350°C under different humidity conditions (RH = 0% and at RH = 100%). The largest structural channels are eight-and ten-rings delimited by corner-sharing SiO4 tetrahedra and ZrO6 octahedra. Under dry conditions, the structure started liberating water at 75°C. At 100°C, when it lost one H2O molecule, elpidite underwent a structural change from space group Pbcm to Cmce. The structure continuously released water up to 225 °C until it became anhydrous. From 225°C to 350°C no structural changes were observed. Associated with the transition from Pbcm to Cmce symmetry, the unit-cell volume reduced by 2.7%. An additional decrease is observed up to 225°C when the contraction reached 3.4% of the starting volume. After release of all H2O molecules, increase of temperature led to gradual expansion of the unit cell from 2940.79(7) Å 3 at 225°C to 2947.4(5) Å 3 at 350°C. Supplementary ex-situ heating experiments showed that the structure was retained up to 950°C but after heating at 1200°C the sample melted. Under humid conditions a similar dehydration-trend similar to that found under a dry N2atmosphere was observed but the structural changes occurred at slightly higher temperatures. Immersion of a dehydrated sample in water for 30 days led to only marginal rehydration and the Cmce symmetry was preserved.