Bis(diphenyldithiophosphinato)lead(II), Pb(S2PPh2)2, was obtained either as a redistribution/decomposition product of Ph2Pb(S2PPh2)2 or directly as a reaction product of Pb(OCOCH3)2-3H2O and NH4S2PPh2. Its crystal and molecular structure was determined by X-ray diffraction. The compound crystallizes in the triclinic space group P1BAR, with cell parameters a = 9.017(2) angstrom, b = 10.839(2) angstrom, c = 12.808(2) angstrom, alpha = 99.48(2)degrees, beta = 90.13(2)degrees, gamma = 97.91(2)degrees, and Z = 2. The monomeric unit contains distorted square-pyramidal PbS4 units. Additionally, each lead atom has two weak lead-sulfur contacts of 327.0 and 344.8 pm with neighboring molecules, lying on the free side of the PbS4 fragment. This leads to molecule pair units which are repeated in a chain polymeric structure. The coordination polyhedron around lead in the polymeric chain can be described as strongly distorted octahedron, with axial positions occupied by a sulfur atom of a neighboring molecule and a sulfur atom of the proper monomeric unit (S...Pb-S 178.0-degrees), or, alternatively, as a psi-caped octahedron, with the stereochemically active electron pair of lead in the capped position.