Three new thioindate-thioantimonates [Ni(en)(3)][In(2)Sb(2)S(7)] (1, en = ethylenediamine), [(Ni(en)(3))](3)(en)[In(6)Sb(6)S(21)] (2), and [Co(tren)InSbS(4)] (3, tren = tris(2-aminoethyl)amine) have been solvothermally synthesized and structurally characterized. Compound 1 contains dimeric [In(2)S(7)] units built of two tetrahedral [InS(4)] units sharing one corner and [SbS(3)] trigonal-pyramids, which are interconnected to form a puckered [In(2)Sb(2)S(7)](n)(2n-) layer with 4-, 5- and 6-heterorings. [Ni(en)(3)](2+) complex cations as structure-directing and charge-balancing agents are located at the interlayer spaces. Compound 2 consists of a 3-D polymeric [In(6)Sb(6)S(21)](n)(6n-) anion, [Ni(en)(3)](2+) cations, free en molecule and a water molecule. The 3-D polymeric [In(6)Sb(6)S(21)](n)(6n-) anion is composed of [In(2)Sb(2)S(8)](n)(4n-) chains and heterometallic [In(2)Sb(2)S(9)] clusters, which are interconnected to give 3-D frameworks with 10-ring helical channels, 14- and 20-ring channels. Compound 3 contains dimeric [In(2)S(6)] units constructed by two tetrahedral [InS(4)] sharing a common edge and [SbS(3)] trigonal-pyramids, which link to form a new [InSbS(4)](n)(2n-) layer with large 10-heterorings. Each [Co(tren)](2+) group is appended within the cavity of the 10-heteroring via one Co-S-Sb bond. 3 represents the first example of the incorporation of transition metal ions into a In-S-Sb framework. Density functional theory calculation for 3 also has been performed, and the optical properties of 1-3 have been characterized by UV-vis spectra.