The complexes, Pb(ChAr(Pri4))(2) (Ch = O (1), S (2); Ar-Pri4 = C6H3-2,6-(C6H3-2,6-Pr-2(i))(2)) were synthesized by alcoholysis and salt metathesis routes and represent the first fully characterized monomeric, two-coordinate, lead dichalcogenolates in the solid state. Structural studies showed that the S-Pb-S angle (77.21(4)degrees) is about 22 degrees narrower than the corresponding O-Pb-O angle. Pb-207 NMR and electronic spectroscopy show that the separation between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) decreases from the bisaryloxo plumbylene to the bisthiolato derivative. Reaction of LiSArMe6 with PbBr2 in a 2:1 ratio led not to Pb(SArMe6)(2), but to a mixture of the monothiolato lead(II) complex, {Pb(Br)(mu-SArMe6)}(2) (3) and the lithium tristhiolato plumbate, LiPb(SArMe6)(3) (4). 3 and 4 were isolated and purified by fractional recrystallization, and both were characterized by X-ray crystallography and spectroscopic studies.