Characterization of the interaction of water with the highly ordered mesoporous solid MCM-41 (pore diameter similar to 2.5 nm) is undertaken with the aid of several techniques (adsorption gravimetry, X-ray diffraction, Fourier transform infrared spectroscopy, and controlled rate-evolved gas analysis). The relatively complex water-MCM-41 interactions are characterized by a type V isotherm indicating an initial repulsive character followed by a capillary condensation step of the adsorbate. This highlights both hydrophobic and hydrophilic properties of this potential model mesoporous adsorbent.