Water intrusion-extrusion isotherms performed at room temperature on hydrophobic pure silica chabazite show that the water-Si-CHA system displays real spring behavior. However, differences in pressure-volume diagrams are observed between the first and the other intrusion-extrusion cycles, indicating that some water molecules interact with the inorganic framework after the first intrusion. (29)Si and especially (1)H solid-state NMR showed the creation of new defect sites upon the intrusion-extrusion of water and the existence of two kinds of water molecules trapped in the supercage of Si-CHA: a first layer of water strongly hydrogen bonded with the silanols of the framework and a subsequent layer of liquidlike physisorbed water molecules undergoing interaction with the first layer. This hydrogen bonding scheme is also supported by X-ray powder diffraction.