Despite the success of electrical stimulation in many areas, including clay or sludge dewatering, extraction of juices from fruit pulp, fracture healing, and targeted drug delivery, the induced transport mechanisms are controlled by unknown factors. While electroosmotic dewatering of clays particles <10 μm is well-known, understanding of how tightly bound water molecules are removed from within the clay interlayers is still incomplete. By performing quasielastic neutron scattering experiments with in situ electric field stimuli on calcium montmorillonite (Ca-Mt) prehydrated at relative humidity (RH) of 58 and 85%, we observed an increase in the water mean residence time, suggesting that hydrogen bonding lifetimes are prolonged under electric field. Assuming that at these RH most all water present resides within the interlayer space of the Ca-Mt, this result indicates strong polarization of the water by the interlayer cation. This electroosmotic induced reorganization has important implications in terms of ion mobility and aqueous chemical reaction mechanisms.