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In porous Prussian blue (PB) analogues, the partially naked central metal atoms found at the cavities surface are responsible for many of their physical properties, among them the adsorption potentials. In the as-synthesized PB analogues, such metal sites stabilize water molecules inside the cavity through coordination bond formation. The filling of the cavity volume is completed with water molecules linked to the coordinated ones through hydrogen bonds formation. Vanadyl-based PB analogue shows quite different features. The metal(V) at the cavities surface has saturated its coordination sphere with the O atom of the vanadyl ion (V=O). In this material, the V=O group preserves enough strong dipole moment to stabilize adsorbed species at the cavity through dipole-dipole and dipole-quadrupole in-

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