A series of di-, tri-, and tetra-nuclear iron-oxido clusters with bis(trimethylsilyl)amide and thiolate ligands were synthesized from the reactions of Fe{N(SiMe3)(2)}(2) (1) with 1 equiv of thiol HSR (R = C6H5 (Ph), 4-(BuC6H4)-Bu-t, 2,6-Ph2C6H3 (Dpp), 2,4,6-(Pr3C6H2)-Pr-i (Tip)) and subsequent treatment with O-2. The trinuclear clusters [{(Me3Si)(2)N}Fe](3)(mu(3)-O){mu-S(4-RC6H4)}(3) (R = H (3a), Bu-t (3b)) were obtained from the reactions of 1 with HSPh or HS(4-(BuC6H4)-Bu-t) and O-2, while we isolated a tetranuclear cluster [{(Me3Si)(2)N}(2)Fe-2(mu-SDpp)](2)(mu(3)-O)(2) (4) as crystals from an analogous reaction with HSDpp. Treatment of a tertrahydrofuran (THF) solution of 1 with HSTip and O-2 resulted in the formation of a dinuclear complex {{(Me3Si)(2)N}(TipS)(THF)Fe](2)(mu-O) (5). The molecular structures of these complexes have been determined by X-ray crystallographic analysis.