The title compound, [dicyclohexyl(sulfanylidene)-λ⁵-phosphanyl]methanol, Cy₂P(=S)CH₂OH (1), was obtained from the reaction between [Cy₂P(CH₂OH)₂]Cl with one molar equivalent of NaOH and an excess of elemental sulfur (powdered). Characterization was by a single-crystal X-ray structure determination as well as IR, and ¹D-NMR (¹H, ¹³C{1H}, ³¹P{1H}), and 2D-NMR (DEPT-135 and HSQC) spectroscopy, ESI mass spectrometry, and elemental analysis. X-ray crystallography on Compound 1 shows the phosphorus atom to be tetrahedrally coordinated within a non-symmetric C₃S donor set but with relatively minor distortions from the ideal geometry. In the molecular packing, hydroxyl-O–H⋯S(thione) hydrogen bonds led to supramolecular helical chains along the b-axis direction.