The first discrete anionic indium thiophosphate complexes are reported. The structures of K-6[In(PS4)(1.5)(PS5)(1.5)] (1), Rb-6[In(PS4)(PS5)(2)] (2), and Cs-6[In(PS4)(1.5)(PS5)(1.5)] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS4](3-) and the new [PS5](3-) ion. The conformation and bonding of the unsymmetric chelate ligand [PS5](3-) to indium give rise to different anions of the general formula [In(PS4)(1+x)(PS5)(2-x)](6-) (x = 0, 0.5). The anionic moiety in K-6[In(PS4)(1.5)(PS5)(1.5)] (1) consists of cocrystallizing lambda-[In(PS4)(2)(PS5)](6-) and Lambda lambda delta-[In(PS4)(PS5)(2)](6-) anions in a ratio of 1:1 (and their enantiomers). In Rb-6[In(PS4)(PS5)(2)] (2), no cocrystallizatzion of anions was observed, and only the Lambda lambda lambda-[In(PS4)(PS5)(2)](6-) anion (and its enantiomer) is present. Cs-6[In(PS4)(1.5)(PS5)(1.5)] (3) shows the same disorder between [PS4](3-) and [PS5](3-) ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Lambda delta delta-[(PS4)(PS5)(2)](6-) anion cocrystallizing with delta-[In(PS4)(2)(PS5)](6-). Additionally, ordered Rb-6[In(PS4)(PS5)(2)] (2) was characterized by P-31 magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.