Photo-degradation of organic pollutants plays an important role in their removal from the environment. This study provides an experimental and theoretical account of the reaction of singlet oxygen O₂(¹Δ_g) with the biodegradable-resistant species of phenol in an aqueous medium. The experiments combine customised LED-photoreactors, high-performance liquid chromatography (HPLC), and electron paramagnetic resonance (EPR) imaging, employing rose bengal as a sensitiser. Guided by density functional theory (DFT) calculations at the M062X level, we report the mechanism of the reaction and its kinetic model. Addition of O₂(¹Δ_g) to the phenol molecule branches into two competitive 1,4-cycloaddition and ortho ene-type routes, yielding 2,3-dioxabicyclo[2.2.2]octa-5,7-dien-1-ol (i.e., 1,4-endoperoxide 1-hydroxy-2,5-cyclohexadiene) and 2-hydroperoxycyclohexa-3,5-dien-1-one, respectively. Unimolecular rearrangements of the 1,4-endoperoxide proceed in a facile exothermic reaction to form the only experimentally detected product, para-benzoquinone. EPR revealed the nature of the oxidation intermediates and corroborated the appearance of O₂(¹Δ_g) as the only active radical participating in the photosensitised reaction. Additional experiments excluded the formation of hydroxyl (HO˙), hydroperoxyl (HO₂˙), and phenoxy intermediates. We detected for the first time the para-semibenzoquinone anion (PSBQ), supporting the reaction pathway leading to the formation of para-benzoquinone. Our experiments and the water-solvation model result in the overall reaction rates of k_r-solvation = 1.21 × 10⁴ M⁻¹ s⁻¹ and k_r = 1.14 × 10⁴ M⁻¹ s⁻¹, respectively. These results have practical application to quantify the degradation of phenol in wastewater treatment.