Half-sandwich iron thiocarboxylate complexes of the general formula CpFe(CO)₂-SCOCH=C(R^¢)(RR^¢¢){R^¢ = H, R^¢¢ = Me, R^¢ = R^¢¢ = Me, R^¢ = H, R^¢¢ = CH=CHMe}) are obtained from the reaction of (l-S_x)[CpFe(CO)₂]₂ (x = 1–5) with the vinyl acid chlorides ClCOCH=C(R^¢)(R^¢¢). The substitution reaction of CpFe(CO)₂SCOCH=C(R)Me with EPh3 produced the monosubstituted complexesCpFe(CO)(EPh₃)SCOCH=C(R)Me (R = Me, E = P, R = H, E = As, Sb). All the new complexes have been characterized by UV-Vis, IR, ¹H-NMR, ¹³C{¹H}-NMR, ³¹P{¹H}-NMR spectroscopy and elemental analysis.The solid state structures and the cyclic voltammetric measurements of CpFe(CO)₂SCOCH=CMe₂ andCpFe(CO)(PPh₃)SCOCH=CMe₂ were determined.