In order to investigate the coordination chemistry of O-alkyl N-aryl thiocarbamate ligands, BiI3 was reacted with two equivalents of MeOC(=S)N(H)Ph in MeCN solution to afford the dinuclear title compound complexes [{I2Bi(μ2-I)2BiI2}{κ1-MeOC(=S)N(H)Ph}4] 1. Compound 1 was characterized by IR, UV and NMR spectroscopy, the formation of a dinuclear framework is ascertained by a single-crystal X-ray diffraction study performed at 100 K.