A series of alcohol-intercalated vanadyl phosphonates VO(HOOCCH2)PO3, CH3(CH2)(n)OH (n = 0, 1, 2, 3, 4), and VO(HOOCCH2)PO3, OH(CH2)(n)OH (n = 3, 4, 5, 6, 8, 10) were prepared in an alcoholic medium. Characterization by X-ray diffraction (XRD), thermogravimetric analysis (TGA), IR spectroscopy, and magnetic measurement is reported. The basal spacing of these lamellar materials increased linearly with the alcohol carboxylic chain length, and pillared material was obtained by dialcohol intercalation. The exchange capacity between alcohol and water is demonstrated and shows that the alcohol OH function is located in the vanadium atom environment, in place of the water molecule that finishes the octahedral coordination of this atom.