Three different zirconium thio and oxothio clusters, characterized by different coordination modes of dithioacetate and/or monothioacetate ligands, were obtained by the reaction of monothioacetic acid with zirconium n-butoxide, Zr((OBu)-Bu-n)(4), in different experimental conditions. In particular, we isolated the three polynuclear Zr-3(mu(3)-SSSCCH3)(2)(SSOCH3)(6) -2(n)BuOH (Zr-3), Zr-4(mu(3)-O)(2)(mu-eta(1)-SOCCH3)(2)(SOCCH3)(8)((OBu)-Bu-n)(2) (Zr-4), and Zr-6(mu(3)-O)(5)(mu-SOCCH3)(2)(mu-OOCCH3)(SOCCH3)(11)((BuOH)-Bu-n) (Zr-6) derivatives, presenting some peculiar characteristics. Zr6 has an unusual star-shaped structure. Only sulfur-based ligands, viz., chelating dithioacetate monoanions and an unusual ethane-1,1,1-trithiolate a group mu(3) coordinating the Zr ions, were observed in the case of Zr-3. 1D and 2D NMR analyses confirmed the presence of differently coordinated ligands. Raman spectroscopy was further used to characterize the new polynuclear complexes. Time-resolved extended X-ray absorption fine structure measurements, devoted to unraveling the cluster formation mechanisms, evidenced a fast coordination of sulfur ligands and subsequent relatively rapid rearrangements.