We report the generation and characterization of a new high-spin iron(IV)-oxo complex supported by a trigonal nonheme pyrrolide platform. Oxygen-atom transfer to [(tpa(Mes))(-) Fe-II](-) (tpa(Ar)=tris(5-arylpyrrol-2-ylmethyl)amine) in acetonitrile solution affords the Fe(III)-alkoxide product [(tpa(Mes2MesO))Fe-III](-) resulting from intramolecular C-H oxidation with no observable ferryl intermediates. In contrast, treatment of the phenyl derivative [(tpa(Ph))Fe-II](-) with trimethylamine N-oxide in acetonitrile solution produces the iron(IV)- oxo complex [tpa(Ph))Fe-IV(O)](-) that has been characterized by a suite of techniques, including mass spectrometry as well as UV- vis, FTIR, Mossbauer, XAS, and parallel mode EPR spectroscopies. Mass spectral, FTIR, and optical absorption studies provide signatures for the iron oxo chromophore, and Mossbauer and XAS measurements establish the presence of an Fe(IV) center. Moreover, the Fe(IV) oxo species gives parallel-mode EPR features indicative of a high-spin, S = 2 system. Preliminary reactivity studies show that the high-spin ferryl tpa(Ph) complex is capable of mediating intermolecular C-H oxidation as well as oxygenatom transfer chemistry.