The HfIV-oxothiocluster, [Hf4(η2-μ2-SAc)4(η2-μ2-SAc)2(η2-μ2-BuO)4(η2-BuO)2(μ3-O)2], was synthesized by reaction of hafnium butoxide with thioacetic acid. The crystal structure shows the presence of a planar tetranuclear Hf4 core, in which the metal atoms are μ3-O bridged and the thioacetate ligands coordinate the Hf ions both through a bridging and a chelating mode. The structural findings are confirmed by multinuclear NMR spectroscopic data.