To fully characterize the Co-III-'nitrene radical' species that are proposed as intermediates in nitrene transfer reactions mediated by cobalt(II) porphyrins, different combinations of cobalt(II) complexes of porphyrins and nitrene transfer reagents were combined, and the generated species were studied using EPR, UV-vis, IR, VCD, UHR-ESI-MS, and XANES/XAFS measurements. Reactions of cobalt(II) porphyrins 1(P1) (P1 = meso-tetraphenylporphyrin (TPP)) and 1(P2) (P2 = 3,5-Di(t)Bu-ChenPhyrin) with organic azides 2(Ns) (NsN(3)), 2(Ts) (TsN3), and 2(Troc) (TrocN(3)) led to the formation of mono-nitrene species 3(Ns)(P1), 3(Ts)(P2), and 3(Troc)(P2), respectively, which are best described as [Co-III(por)(NR ''(center dot-))] nitrene radicals (imidyl radicals) resulting from single electron transfer from the cobalt(II) porphyrin to the 'nitrene' moiety (Ns: R '' = -SO2-p-C6H5NO2; Ts: R '' = -SO2C6H6; Troc: R '' = -C(O)OCH2CCl3). Remarkably, the reaction of 1(P1) with N-nosyl iminoiodane (PhI=NNs) 4(Ns) led to the formation of a bis-nitrene species 5(Ns)(P1). This species is best described as a triple-radical complex [(por ''(center dot-))Co-III(NR ''(center dot-))(2)] containing three ligand-centered unpaired electrons: two nitrene radicals (NR?(-)) and one oxidized porphyrin radical (por(center dot-)). Thus, the formation of the second nitrene radical involves another intramolecular one-electron transfer to the "nitrene" moiety, but now from the porphyrin ring instead of the metal center. Interestingly, this bis-nitrene species is observed only on reacting 4(Ns) with 1(P1). Reaction of the more bulky 1(P2) with 4(Ns) results again in formation of mainly mono-nitrene species 3(Ns)(P2) according to EPR and ESI-MS spectroscopic studies. The mono- and bis-nitrene species were initially expected to be five- and six-coordinate species, respectively, but XANES data revealed that both mono- and bis-nitrene species are six-coordinate Oh species. The nature of the sixth ligand bound to cobalt(III) in the mono-nitrene case remains elusive, but some plausible candidates are NH3, NH2-, NsNH(-), and OH-; NsNH(-) being the most plausible. Conversion of mono-nitrene species 3(Ns)(P1) into bis-nitrene species 5(Ns)(P1) upon reaction with 4(Ns) was demonstrated. Solutions containing 3(Ns)(P1) and 5(Ns)(P1) proved to be still active in catalytic aziridination of styrene, consistent with their proposed key involvement in nitrene transfer reactions mediated by cobalt(II) porphyrins.