Four nickel clusters, cyclo-[{Ni(μ-S(i)Pr)(μ-SMe)}(6)] (1), cyclo-[{Ni(μ-StBu)(μ-SMe)}(6)] (2), cyclo-[{Ni(μ-S(i)Pr)(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.