The pentamethylcyclopentadienyl substituted ironbismuth halides [Bi{FeCp*(CO)(2)}X-2] [X = Cl (1), Br (2), I (3); Cp* = eta(5)-C5Me5] were synthesized starting from [FeCp*(CO)(2)](2) and BiX3 (X = Cl, Br), followed by halogen exchange reaction with KI in case of 3. From a reaction mixture of [FeCp*(CO)(2)](2) with BiCl3 in CH2Cl2 to which CH3CN had been added, a novel coordination polymer of the formula [FeCp*(CO)(2)(CH3CN)](2n)[Bi4Cl14](n) (4) was isolated. The change of the molar ratio from 1:1 to 1:2 in the reaction of [FeCp*(CO)(2)](2) with BiBr3 afforded the novel ionic complex [{FeCp*(CO)(2)Br](2)[Bi6Br22{FeCp*(CO)(2)}]center dot CH2Cl2 (5 center dot CH2Cl2). It is demonstrated that treatment of [FeCp*(CO)(2)X] (X = Cl, Br) with BiCl3 and BiBr3, respectively, is a more convenient route to synthesize the new halido bismuthates 4 and 5.