Four nickel clusters, cyclo-[{Ni(μ-SⁱPr)(μ-SMe)}₆] (1), cyclo-[{Ni(μ-StBu)(μ-SMe)}₆] (2), cyclo-[{Ni(μ-SⁱPr)(μ-SEt)}₆] (3) and cyclo-[{Ni(μ-StBu)(μ-SEt)}₁₀] (4), based on thiolate ligands have been successfully synthesized and characterized by elemental analysis, FT-IR spectra, UV-vis-NIR spectra, powder X-ray diffraction and single-crystal X-ray diffraction. Intriguingly, the SMe and SEt ligands are generated from solvothermal in situ ligand synthesis through the cleavage of the S–S bond respectively. The four nickel thiolate clusters exhibit tiara-like frameworks consisting of two different types of thiolate ligands.