Supertetrahedral compounds of chalcogenometalates (T3 cluster compounds) integrated with Ni-bpy (bpy = 2,2′-bipyridine) complex were prepared by a solvothermal technique. The compound [Ni(bpy)₃]₃[H₄In₁₀S₂₀]·bpy·2EG·6H₂O (Mb-InS-1) (EG = ethylene glycol) consists of discrete T3 clusters of [H₄In₁₀S₂₀]⁶⁻ with three [Ni(bpy)₃]²⁺ cations. The compound [Ni(bpy)₃]₂[H₂In₁₀S₁₉]·bpy·2HEA·2H₂O (Mb-InS-2) (EA = ethanolamine) is a 1-D polymer, in which zigzag T3 cluster chains are charge balanced by metal-bpy complex cations. The compound [Ni(bpy)₃]₇[H₄In₄₀S₇₄]·7Hbpy·3HEA·8H₂O (Mb-InS-3) is a 2-D T3 polymer with cation layers of [Ni(bpy)₃]²⁺. Integrating M-bpy complex cations into chalcogenido structures has been made with the aim of improving the photoabsorption of the materials. The electronic spectra showed the new bands of cation–anion charge-transfer (CACT) that is mainly caused by the SH–C(py) contacts between the InS T3 supertetrahedral clusters and the [Ni(bpy)₃]²⁺ cations.