Three metal complexes [Cu^I₆(atdm)₆] (1), [Cu^I(Hatd)(H₂atd)] (2) and [H₃O][Co^II₄Co^III₂Cl₃(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 Cu^I 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.