Vanadyl(IV) phosphite, VOHPO3 . 1.5H(2)O, was synthesized by reduction of V2O5 in refluxing alcohol solutions (ethyl, isopropyl, and isobutyl alcohols) with subsequent addition of H3PO3. X-ray diffraction suggests an orthorhombic space group. Magnetic susceptibility data indicate the presence of exchange coupled vanadyl dimers associated with face-shared vanadyl octahedra similar to vanadyl hydrogen phosphate hemihydrate, VOHPO4 . 0.5H(2)O. Vanadyl(IV) phosphite is a layered solid with an interlayer spacing of 7.27 Angstrom. n-Alkylamines intercalated into the layered structure as single or double layers depending on the amine-to-host ratio, and the interlayer spacings, d (Angstrom), increased linearly with the carbon number, n(c), as d = 7.72 + 0.85n(c) (monolayers), and d = 6.49 + 1.82n(c) (bilayers).