Synthesis and characterisation of ether adducts of bis(amidinate) FeII complexes are described [amidinate = 2,6‐iPr2C6H3–NC(Ph)N–Ph]. The isolation of these five‐coordinate complexes contrasts with the homoleptic bis(amidinate) Fe complexes obtained previously with the sterically more demanding amidinate ligands 2,6‐iPr2C6H3–NC(Ph)N–Ar (Ar = 2,6‐iPr2C6H3, 2,6‐Me2C6H3) The more accessible ether adducts show enhanced reactivity towards Lewis bases and towards the π‐acid carbon monoxide. Reaction with excess amounts of CO results in carbonyl insertion into the Fe–N bonds, thereby giving rise to a diamagnetic bis(CO) adduct supported by two carbamoyl ligands.