Swelling of layered smectite particles causes changes in the interlayer repetition basal distance (d-spacing) as a function of temperature and humidity allowing for their application in a number of different fields ranging from the food industry to waste management. Here we will use the synthetic smectite fluorohectorite as model to understand the water interactions with different interlayer cations and how these interatctions change as a function of relative humidity (RH) . Three samples will be studied Na- fluorohectorite, Li-fluorohectorite and Ni-fluorohectorite, where Na, Li and Ni are the respective interlayer cation, each at two different hydration state. The main objectives of the present study are to determine the influence of the interlayer cation in the water mobility as well as to follow how the dynamics and geometrical environment of the intercalated water is modified by the hydration process.