An ionic crystal K-2[Cr3O(OOCC2H5)(6)(H2O)(3)](2)[alpha-SiW(12)O(4)o].3H(2)O (1a) is synthesized by the complexation of a Keggin-type polyoxometalate of [alpha-SiW12O40](4-) with K+ and a macrocation of [Cr3O-(OOCC2H5)(6)(H2O)(3)](+). Compound is possesses both hydrophilic and hydrophobic channels in the crystal lattice. The 3 mol mol(-1) of the water of crystallization in is resides in the hydrophilic channel. The water of crystallization is removed by the evacuation at 303 K to form the guest-free phase 1b with small changes in the lattice lengths (+/- 0.2 angstrom). The water sorption profile is reproduced by the single rate constant. Therefore, the water sorbed probably resides in the hydrophilic channel. Compound 1b sorbs various kinds of polar organic molecules, and the amounts of <= C-3 alcohols are comparable to or larger than that of water, while chlorocarbons with no hydrogen-bonding ability and nonpolar molecules are excluded. Thus, 1b showed the amphiphilic sorption property. The states of the polar organic molecules sorbed in 1b have been quantitatively investigated using ethanol as a probe molecule. The IR, NMR, and single-crystal X-ray diffraction studies combined with the sorption kinetics reveal that ethanol molecules are mainly sorbed into the hydrophilic channel at P/P-0 <= 0.5, while the sorption into the hydrophobic channel is dominant at P/P-0 >= 0.6. Thus, it is demonstrated that ethanol molecules enter both hydrophilic and hydrophobic channels of 1b.