Reaction of equimolar amounts of [Bi(OtBu)3] and [Cp2ReH] yields [Cp2Re-Bi(OtBu)2], 1, when the reaction time is kept short. Treatment of [BiOCH(CF3)2}3(thf)]2 with four equivalents of [Cp2ReH] leads to the heterotrinuclear complex [(Cp2Re)2BiOCH(CF3)2}], 4, with two Re- Bi bonds. A complex with a Bi-Fe bond was obtained in the reaction between [Cp(CO)2Fe]2 and [Bi(OAc)3]: [Cp(CO)2Fe-Bi(OAc)2], 5, was formed and found to crystallize as a dimer. The structures of 1 and 4 were also investigated