Abstract: The in-depth perturbation of vicinal water by the surfaces of montmorillonite layers was investigated by relating the swelling pressure, Π, of the montmorillonite layers to the H-O-H bending frequency, ν2, of the interlayer water. For this purpose, an oriented montmorillonite gel was deposited on a porous filter in an environmental chamber. On its underside the filter was in contact with a solution maintained at atmospheric pressure. By admitting nitrogen gas at a known pressure to the environmental chamber, water was squeezed from the gel into the solution until equilibrium was reached and Π equalled the applied pressure. Then the gel was divided into 2 parts. One part was used for the gravimetric determination of the water content, mw/mc. It was possible, therefore, to determine mw/mc as a function of Π. The other part of the sample was transferred to an FTIR spectrometer where the ν2 of the water within it was measured by attenuated total reflectance. Thus, the same samples were used to determine the dependence of both Π and ν2 on mw/mc. It was found that Π and ν2 were both exponential functions of mc/mw and so a linear relation was found between ln(Π + 1) and ln(ν2/ν2°), where ν2° is the H-O-H bending frequency of bulk water. These results strongly support the conclusion that the in-depth perturbation of the water by the surfaces of the montmorillonite layers is primarily responsible for both the development of Π and the departure of ν2 from ν2°.