The phenyl iron complex of 5,10,15-tritolylcorrole was prepared by reaction of the starting chloro iron complex with phenylmagnesium bromide in dichloromethane. The organometallic complex was fully characterized by a combination of spectroscopic methods, X-ray crystallography, and density functional theory (DFT) calculations. All of these techniques support the description of the electronic structure of this phenyl iron derivative as a low-spin iron(IV) coordinated to a closed-shell corrolate trianion and to a phenyl monoanion. Complete assignments of the H-1 and C-13 NMR spectra of the phenyl iron derivative and the starting chloro iron complex were performed on the basis of the NMR spectra of the regioselectively beta-substituted bromo derivatives and the DFT calculations.