In this work, we report the first computational investigation on the structure and properties of the (peroxo)diiron(III) intermediate of the AurF enzyme. Our calculations predict that, in the oxidized state of the AurF enzyme, the peroxo ligand is depicted in a mu-1,1-coordination mode with a protonated bridging ligand and is not in a mu-eta(2):eta(2) or mu-1,2 mode. Computed spectral data for the mu-1,1-coordination mode correlate well with experimental observations and unravel the potential of the energetics-spectroscopic approach adapted here.