Oxidation of the half-sandwich MnI complexes Cp(CO)2Mn(NHC) bearing dialkyl-, arylalkyl- and diarylsubstituted N-heterocyclic carbene ligands (NHC = IMe, IMeMes, IMes) affords the corresponding stable MnII radical cations [Cp(CO)2Mn(NHC)](BF4) isolated in 92–95% yield. Systematic X-ray diffraction studies of the series of MnI and MnII NHC complexes revealed the expected characteristic structural changes upon oxidation, namely the elongation of the Mn–CO and Mn–NHC bonds as well as the diminution of the OC–Mn–CO angle. ESR spectra of [Cp(CO)2Mn(IMes)](BF4) in frozen solution (CH2Cl2/toluene 1 : 1, 70 K) allowed the identification of two conformers for this complex and their structural assignment using DFT calculations. The stability of these NHC complexes in both metal oxidation states, moderate oxidation potentials and the ease of detection of MnII species by a variety of spectroscopic techniques (UV-Vis, IR, paramagnetic 1H NMR, and ESR) make these compounds promising objects for applications as redox-active organometallic fragments.