Three metal complexes [CuI6(atdm)6] (1), [CuI(Hatd)(H2atd)] (2) and [H3O][CoII4CoIII2Cl3(atd)6]·H2O (3) [atdm = 4-dimethylamino-6-anilino-1,3,5-triazine-2-thiolate, H2atd = 6-anilino-1,3,5-triazine-2,4-dithiol, atdH2 = 6-anilino-1,3,5-triazine-2,4(1H,3H)-dithione] have been solvothermally synthesized. The luminescent complexes 1 and 2 provide remarkable structural diversity depending on different reaction solutions. Complex 1 consists of a discrete pseudohexagonal prismatic [Cu6S6] core that can be described as two stacked, chair-shaped [Cu3S3] rings bound together by the C–N bridges of the atdm ligands, in which the atdm ligand was generated via in situ amination of H2atd in the presence of DMF solution. Whereas complex 2 is a 2D (4,4) net based on single node CuI ions crystallized in acetonitrile, in which H2atd ligands exist in the thione form atdH2 and the partially deprotonated form atdH. Complex 3 has a two-fold interpenetrated (10,3)-a topological network based on unprecedented cobalt-centered trigonal-bipyramidal [Co6(atd)6] building blocks, linked by Cl− double-bridges and showing oriented effects of aniline side groups. IR spectra, elemental analyses and XRD analyses confirmed the phase-purities of the as-synthesized complexes. The photoluminescence properties of 1 and 2 in the solid state and the magnetic properties of 3 are investigated. A discussion of the crystal structures, as well as the coordination properties of the multifunctional sulfur-containing ligands upon different geometries of the central units, is also provided.