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Abstract: The reaction of the complex Re2(CO)4(NO)2Cl4 (1) with NaSCMe3 (2) (in THF or MeCN, 65–80C, 24 h) was studied at different ratios of the reagents (from 1∶2 to 1∶6). At the reagent ratio of 1∶2, the binuclear complex Re2(CO)4(NO)2Cl2(μ-SCMe3)2 (3) was obtained as a mixture ofsyn andanti isomers (3a and3b, respectively) containing Re2S2 fragments with different structures (the butterfly-like structure in3a and the planar fragment in3b). When the initials were taken in ratios from 1∶4 to 1∶6, two compounds were isolated: the binuclear complex Re2(CO)4(NO)2(μ-SCMe3)2(μ-S)4 (cocrystallized as a mixture ofsyn andanti isomers,4a and4b, respectively) and the triangular cluster Re3(CO)3(NO)3(μ-SCMe3((μ3-S)(μ3-Cl) (5). Apparently, complex4 is formed in the course of isolation as a result of elimination of SR2 from the unstable tetrathiolate dimer Re2(CO)4(NO)2(SCMe3)2(μ-SCMe3)2 (6). Cluster5 is the product of the reaction between compounds3 and4. Products of interaction of compound6 with silica gel upon column chromatography of the reaction mixture were studied. Four complexes containing hydroxy and oxo bridging groups, (CO)2(NO)Re(μ-SCMe3)2(μ-OH)Re(SCMe3)(CO)(NO) (7), (CO)3(NO)3RE3(μ-SCMe3)3(μ3-SCME3)(μ3-O) (8), [(CO)2(NO)2Re2(SCMe3)2(μ-SCMe3)2(μ-OH)][Na(THF)(Et2O)] (9), and [(CO)2(NO)2Re2(SCMe3)2(μ-SCMe3)2(μ-OH)]2−[Na(H2O)6][H5O2] (10), were isolated. The structures of complexes3, 4, 5, 7, 8, 9, and10 were established by X-ray diffraction study.