Reaction of Mes(3)In (Mes = 2,4,6-trimethylphenyl) with tert-butyl mercaptan, tert-amyl mercaptan, 2-tert-butylthiophenol, and triphenylsilanethiol yields [Mes(2)In(mu-SR)](2) (R = t-Bu (1), tert-amyl (2), 2-t-BuC(6)H(4) (3), and SiPh(3) (4)). A trimeric indium thiolate, [Me(2)In(mu-SSiPh(3))](3) (5), is isolated from the reaction of Me(3)In with HSSiPh(3). The first structures of di- and trimeric indium thiolato species, 1, 2, 4, and 5, have been determined. The structure of 1 was determined in the space group C2/c (No. 15) with cell constants a 28.809(6) Angstrom, b = 9.041(2) Angstrom, c = 18.156(5) Angstrom, beta = 110.24(2)degrees, V = 4437(2) Angstrom(3), and Z = 8; R = 5.40%, R(W) = 5.67%. 2 and 4 crystallize as dimers in the space group (No. 2). For 2 : a = 11.631(7) Angstrom, b = 12.866(3) Angstrom, c = 15.767(5) Angstrom, alpha = 90.09(2)degrees, beta = 93.70(4)degrees, gamma = 105.13(3)degrees, V = 2273(1) Angstrom(3), Z = 4, R = 8.1%, R(W) = 7.4%. For 4 : a = 12.423(3) Angstrom, b = 13.019(3) Angstrom, c = 14.126(2) Angstrom, alpha = 91.50(1)degrees, beta = 113.23(1)degrees, gamma = 117.72(2)degrees, V = 1795.8(6) Angstrom(3), Z = 2, R = 3.75%, R(W) = 4.3%. In 1, 2, and 4, the (InS)(2) core is planar with the alkyl groups on S oriented in a transoid fashion. 5 exists as a trimer in the space group (No. 2) : a = 15.012(5) Angstrom, b = 17.784(5) Angstrom, c = 24.838(8) Angstrom, alpha = 76.23(2)degrees, beta = 83.03(3)degrees, gamma = 69.84(2)degrees, V = 6040(3) Angstrom(3), Z = 4 (trimers), R = 5.99%, R(W) = 5.34%.