Vinyl selenocarboxylato iron complexes of the formula CpFe(CO)(2)SeCOCH=C(R1)(R2) {R1 = H, R2 = Me, R1 = R2 = Me, R1 = H, R2 = CH=CHMe} are synthesized by the reaction of (mu-Se)[CpFe(CO)(2)](2) with the corresponding vinyl acid chlorides ClCOCH=C(R1)(R2). Photolytic substitutions of CpFe(CO)(2)SeCOCH=CMe2 with EPh3 gave the monosubstituted complexes CpFe(CO)(EPh3)SeCOCH=CMe2 (E = P, As, Sb) in good yields. The new complexes have been characterized by UV-Vis, IR, H-1-NMR, C-13{H-1}-NMR, Se-77{H-1}-NMR, P-31{H-1}-NMR spectroscopy and elemental analysis. The solid state structures of CpFe(CO)(2)SeCOCH=CMe2 and CpFe(CO)(AsPh3)SeCOCH=CMe2 were determined by X-ray crystallography. The cyclic voltammetric measurements of CpFe(CO)(2)SeCOCH=CMe2 were recorded. Graphic abstract Vinyl selenocarboxylato iron complexes of the formula CpFe(CO)(2)SeCOCH=C(R1)(R2) {R1 = H, R2 = Me, R1 = R2 = Me, R1 = H, R2 = CH=CHMe} are synthesized by the reaction of (mu-Se)[CpFe(CO)(2)](2) with the corresponding vinyl acid chlorides ClCOCH=C(R1)(R2). Photolytic substitutions of CpFe(CO)(2)SeCOCH=CMe2 with EPh3 gave the monosubstituted complexes CpFe(CO)(EPh3)SeCOCH=CMe2 (E = P, As, Sb) in good yields. The new complexes have been characterized by UV-Vis, IR, H-1-NMR, C-13{H-1}-NMR, Se-77{H-1}-NMR, P-31{H-1}-NMR spectroscopy and elemental analysis. The solid-state structures of CpFe(CO)(2)SeCOCH=CMe2 and CpFe(CO)(AsPh3)SeCOCH=CMe2 were determined by X-ray crystallography and the cyclic voltammetric measurements of CpFe(CO)(2)SeCOCH=CMe2 were recorded.