In this paper, we have demonstrated that symmetric complexes [(edt)2Mo2O2(µ-S)2Ag2(dppm)2] (2, edt = 1,2-ethanedithiolate dianion, dppm = bis(diphenylphosphino)methane) and [(µ-Cl)2Ag4(µ3-Cl)2(dppm)2]·4DMF (3, DMF = N,N-dimethylformamide), were generated by combining a dinuclear molybdnum precursor [nPr4N]2[(edt)2Mo2O2(µ-S)2] (1) with two equimolar AgNO3 and dppm in DMF and CH2Cl2 mixed solutions. Treatment of complex 1 with AgBr in acetonitrile followed by addition of (NH4)2S produced a dodecanuclear Mo–Ag–S cage cluster [nPr4N]2[{Mo2Ag2S2O2(edt)2}3(µ6-S)]·1.5CH3CN (4). Complexes 2−4 have been characterized by were characterized by infrared, 1H NMR, UV-vis, and fluorescence spectroscopies. Moreover, molecular structures of complexes 2−4 have been established by single-crystal X-ray crystallography.