For a series of (1-hydroxyalkyl)dimethylphosphine sulfides Me2P(S)C(OH)R1R2 the molecular structures have been determined. The crystallographic results obtained are as follows. Me2P(S)C(OH)Me2; monoclinic, P21/n, a = 10.910(3) A, b = 6.340(2) A, c = 11.886(3) A, β = 96.47(2)°, V = 816.9 A3, Z = 4. Me2P(S)C(OH)(CH2)5: orthorhombic, P212121, a = 8.683(3) A, b = 9.474(3) A, c = 12.730(3) A, V = 1047.2 A3, Z = 4. Me2P(S)C(OH)(Me)C(O)Me: orthorhombic, P212121, a = 7.664(3) A, b = 10.354(2) A, c = 11.838(3) A, V = 939.4 A3, Z = 4. Me2P(S)C(OH)(Ph)C(O)Ph: monoclinic, P21/n, a = 8.400(3) A, b = 10.343(3) A, c = 17.784(4) A, β = 101.97(3)°, V = 1511.5 A3, Z = 4. Me2P(S)C(OH)(H)C(O)(OH): triclinic, P1, a = 6.145(2) A, b = 11.268(4) A, c = 12.126(3) A, α = 110.64(2)°, β = 103.64(2)°, γ = 94.88(2)°, V = 750.4 A3, Z = 4. The principal values of the phosphorus nuclear magnetic shielding tensor have been determined by 31P solid-state CP MAS NMR spectroscopy. The similar structures of the compounds around the P atom...