The reaction of bismuth(III) chloride with [PhCH(2)NMe(3)](2)[Fe(CO)(4)] at a ratio of 2:1 in acetonitrile yields the iron carbonyl-bismuth chloride adduct [PhCH(2)NMe(3)](2)[Bi2Cl4-(mu-Cl)(2){mu-Fe(CO)(4)}] cleanly in high yield. The complex consists of two BiCl3 groups bridged by an [Fe(CO)(4)](2-) unit. Two chloride ligands are shared between the Bi atoms, producing square-pyramidal coordination at bismuth and octahedral coordination at the iron center. The production of this complex represents the synthesis of a stable adduct of a highly nucleophilic metal carbonyl anion with a strongly Lewis acidic main group halide. The compound C24H32N2O4Bi2Cl6Fe crystallizes in the orthorhombic space group Pba2 (No. 32) with cell parameters a = 14.624(3) Angstrom, b = 17.010(3) Angstrom, c = 7.1990(10) Angstrom, V = 1790.8(5) Angstrom(3), and Z = 2.