Herein, we report the preparation and characterization of two diiron carbonyl complexes with ethyldiphenylphosphine or dicyclohexylphenylphosphine. Me3NO-driven decarbonylation of complex [Fe-2(CO)(6)(mu-SCH2CH2CH2S)] (1) with the corresponding phosphine ligands afforded the products [Fe-2(CO)(5)(Ph2PCH2CH3)(mu-SCH2CH2CH2S)] (2) and [Fe-2(CO)(5)PhP(C6H11)(2)(mu-SCH2CH2CH2S)] (3) in 91% and 84% yields, respectively. The structures of complexes 2 and 3 have been identified by spectroscopy, elemental analysis, and X-ray diffraction analysis. Moreover, the electrochemistry was investigated by cyclic voltammetry.