The synthesis and structural characterization of several lithium thiolates are reported. Formation of discrete species can be achieved by careful variation of ligand size and donor hapticity, as exemplified by the monomeric formulation of Li(PMDTA)STrityl (PMDTA = N,N,N’,N ",N "-pentamethyldiethylenetriame, Trityl = CPh(3)), 1, and Li(PMDTA)STrip, 2 (Trip = 2,4,6-iPr(3)C(6)H(2)), versus the dimeric species [Li(THF)(2)STrityl](2), 3, and [Li(TMEDA)STrip](2), 4 (TMEDA = N,N,N ",N "-tetramethylethylenediamine). By control of the stoichiometry of the donor, the first trimeric lithium thiolate [Li(THF)SMes*](3), 5 (Mes* = 2,4,6-tBu(3)C(6)H(2)), exhibiting a six-membered ring system and rare three-coordinate lithium centers, becomes available. In contrast, use of a crown ether leads to the isolation of the monomeric contact ion pair Li(12-crown-4)STrityl, 6, while employing the cumbersome-SMes* ligand allows for the isolation of the first solvent-separated lithium thiolate [Li(12-crown-4)(2)][SMes*], 7. All compounds were prepared by reacting the respective thiols with nBuLi in the presence of various donor adjuncts.