Na/Pb alloy reduction of the (perfluoroisopropyl)iridium complex Cp*(CO)IrI[CF(CF3)2] afforded the first example of a bis(trifluoromethyl)carbene complex, Cp*(CO)Ir=C(CF3)2, which has been crystallographically characterized. Further reduction of this carbene complex with KC8 yielded the perfluoroallene iridium complex Cp*Ir(CO)(η2‐CF2CCF2). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)