The direct reaction of liquid (or melted solid) 1-alkanols or 1,omega-alkanediols with solid finely ground VOPO(4). 2H(2)O in a microwave field leads to layered complexes of the composition VOPO(4).2C(n)()H(2)(n)()(+1)OH (n = 1-18) or VOPO(4).C(n)()H(2)(n)()(OH)(2) (n = 2-10), respectively. The results of X-ray diffraction analysis show that the structures of all of these polycrystalline complexes (intercalates) retain the original layers of (VOPO(4))(infinity). The molecules of alcohols are placed between the host layers in a bimolecular way, being anchored to them by donor-acceptor bonds between the oxygen atom of an OH group and a vanadium atom as well as by hydrogen bonds. The molecules of diols, on the other hand, using similar bonds, form, in monomolecular arrangement, bridges linking the adjacent layers of the host. The aliphatic chains of both intercalated alcohol and diol molecules possess all-trans configurations, and their axes are perpendicular to the host layers.