Pulse radiolysis and FT-IR smog chamber experiments were used to investigate the atmospheric fate of C₆H₅O(•) radicals. Pulse radiolysis experiments gave σ(C₆H₅O(•))_{235 nm} = (3.82 ± 0.48) × 10^-17 cm² molecule^-1, k(C₆H₅O(•) + NO) = (1.88 ± 0.16) × 10^-12, and k(C₆H₅O(•) + NO₂) = (2.08 ± 0.15) × 10^-12 cm³ molecule^-1 s^-1 at 296 K in 1000 mbar of SF₆ diluent. No discernible reaction of C₆H₅O(•) radicals with O₂ was observed in smog chamber experiments, and we derive an upper limit of k(C₆H₅O(•) + O₂) < 5 × 10^-21 cm³ molecule^-1 s^-1 at 296 K. These results imply that the atmospheric fate of phenoxy radicals in urban air masses is reaction with NO_x. Density functional calculations and gas chromatography-mass spectrometry are used to identify 4-phenoxyphenol as the major product of the self-reaction of C₆H₅O(•) radicals. As part of this study, relative rate techniques were used to measure rate constants for reaction of Cl atoms with phenol [k(Cl + C₆H₅OH) = (1.93 ± 0.36) × 10^-10], several chlorophenols [k(Cl + 2-chlorophenol) = (7.32 ± 1.30) × 10^-12, k(Cl + 3-chlorophenol) = (1.56 ± 0.21) × 10^-10, and k(Cl + 4-chlorophenol) = (2.37 ± 0.30) × 10^-10], and benzoquinone [k(Cl + benzoquinone) = (1.94 ± 0.35) × 10^-10], all in units of cm³ molecule^-1 s^-1. A reaction between molecular chlorine and C₆H₅OH to produce 2- and 4-chlorophenol in yields of (28 ± 3)% and (75 ± 4)% was observed. This reaction is probably heterogeneous in nature, and an upper limit of k(Cl₂ + C₆H₅OH) ≤ 1.9 × 10^-20 cm³ molecule^-1 s^-1 was established for the homogeneous component. These results are discussed with respect to the previous literature data and to the atmospheric chemistry of aromatic compounds.