ortho-Hydroxylation of aromatic compounds by non-heme Fe complexes has been extensively studied in recent years by several research groups. The nature of the proposed oxidant varies from Fe-III-OOH to high-valent Fe-IV=O and Fe-V=O species, and no definitive consensus has emerged. In this comprehensive study, we have investigated the ortho-hydroxylation of aromatic compounds by an iron complex using hybrid density functional theory incorporating dispersion effects. Three different oxidants, Fe-III-OOH, Fe-IV=O, and Fe-V=O, and two different pathways, H-abstraction and electrophilic attack, have been considered to test the oxidative ability of different oxidants and to underpin the exact mechanism of this regiospecific reaction. By mapping the potential energy surface of each oxidant, our calculations categorize FeIII-OOH as a sluggish oxidant, as both proximal and distal oxygen atoms of this species have prohibitively high barriers to carry out the aromatic hydroxylation. This is in agreement to the experimental observation where Fe-III-OOH is found not to directly attack the aromatic ring. A novel mechanism for the explicit generation of non-heme Fe-IV=O and Fe-V=O from isomeric forms of Fe-III-OOH has been proposed where the O center dot center dot center dot O bond is found to cleave via homolytic (Fe-IV=O) or heterolytic (Fe-V=O) fashion exclusively. Apart from having favorable formation energies, the Fe-V=O species also has a lower barrier height compared to the corresponding Fe-IV=O species for the aromatic ortho-hydroxylation reaction. The transient Fe-V=O prefers electrophilic attack on the benzene ring rather than the usual aromatic C-H activation step. A large thermodynamic drive for the formation of a radical intermediate is encountered in the mechanistic scene, and this intermediate substantially diminishes the energy barrier required for C-H activation by the Fe-V=O species. Further spin density distribution and the frontier orbitals of the computed species suggest that the Fe-IV=O species has a substantial barrier height for this reaction, as the substrate is coordinated to the metal atoms. This coordination restricts the C-H activation step by Fe-IV=O species to proceed via the pi-type pathway, and thus the usual energy lowering due to the low-lying quintet state is not observed here.