For a series of (l-hydroxyalkyl)dimethylphosphine sulfides Me(2)P(S)C(OH)R(1)R(2) the molecular structures have been determined. The crystallographic results obtained are as follows. Me(2)P(S)C(OH)Me(2); monoclinic, P2(1)/n, a = 10.910(3) Angstrom, b = 6.340(2) Angstrom, c = 11.886(3) Angstrom, beta = 96.47(2)degrees, V = 816.9 Angstrom(3), Z = 4. Me(2)P(S)C(OH)(CH2)(5) : orthorhombic, P2(1)2(1)2(1), a = 8.683(3) Angstrom, b = 9.474(3) Angstrom, c = 12.730(3) Angstrom, V = 1047.2 Angstrom(3), Z = 4. Me(2)P(S)C(OH)(Me)C(O)Me : orthorhombic, P2(1)2(1)2(1), a = 7.664(3) Angstrom, b = 10.354(2) Angstrom, c = 11.838(3) Angstrom, V = 939.4 Angstrom(3), Z = 4. Me(2)P(S)C(OH)(Ph)C(O)Ph : monoclinic, P2(1)/n, a = 8.400(3) Angstrom, b = 10.343(3) Angstrom, c = 17.784(4) Angstrom, beta = 101.97(3)degrees, V = 1511.5 Angstrom(3), Z = 4. Me(2)P(S)C(OH)(H)C(O)(OH) : triclinic, , a = 6.145(2) Angstrom, b = 11.268(4) Angstrom, c = 12.126(3) Angstrom, alpha = 110.64(2)degrees, beta = 103.64(2)degrees, gamma = 94.88(2)degrees, V = 750.4 Angstrom(3), Z = 4. The principal values of the phosphorus nuclear magnetic shielding tensor have been determined by P-31 solid-state CP MAS NMR spectroscopy. The similar structures of the compounds around the P atom and symmetry considerations allow a prediction of the orientation of the shielding tensor principal axes in the molecular framework. Quantum chemical calculations applying the IGLO method support these results. By application of three independent methods (X-ray structure analysis, solid-state NMR spectroscopy, and quantum chemical calculations) the influence of intermolecular interactions on the nuclear magnetic shielding can be clearly shown.