The electrochemical oxidation of anodic indium metal in an acetonitrile solution of phosphinothiol ligands affords [In{2-(Ph2P)C6H4S}(3)] (1), [In{2-(Ph2P)-6-(Me3Si)C6H3S)}(2){2-(Ph2PO)-6-Me3Si)C6H3S}] (2), [In{2-(Ph2PO)-6-(Me3Si)C6H3S)3] (3), and [NMe4][In{PhP(C6H4S-2)(2)}(2)]. CH3CN (4) complexes exhibiting distorted six-coordinate geometries based on {InS3P3}, {InS3P2O}, and {InS4P2} cores, respectively. In all cases, the In-P bond distances are anomalously long, presumably as a consequence of steric crowding. The anion of 4 provides an unusual example of an In(III)-thiolate coordination complex ion. Crystal data: 1, C54H42InP3S3, monoclinic, P2(1)/c, a = 16.6579(1) Angstrom, b = 12.6628(2) Angstrom, c = 22.5520(3) Angstrom, beta = 96.42(1)degrees, V = 4727.15(1) Angstrom(3), Z = 4, 6176 reflections, R = 0.0579; 2, C63H66InOP3S3Si3, monoclinic, P2(1)/c, a = 11.53090(10) Angstrom, b = 26.2505(3) Angstrom, c = 20.4206(2) Angstrom, beta = 94.0870(10)degrees, V = 6165.43(11) Angstrom(3), Z = 4, 10 699 reflections, R = 0.0621; 4, C42H41InN2P2S4, monoclinic, P2(1), a = 13.0052(2) Angstrom, b = 11.2240(2) Angstrom, c = 14.3070(3) Angstrom, beta = 93.190(1)degrees V = 2085.16(7) Angstrom(3), Z = 2, 6651 reflections, R = 0.0352.