The nature of the intermediate(s) in the aromatic S(,RN)1 reaction has been studied by two approaches: The reactivity of phenyl radical, generated from an unambiguous source, has been compared to the phenyl radical intermediate in the S(,RN)1 reaction. In the second approach, an intramolecular radical rearrangement was utilized for both diagnostic and kinetic purposes;Evidence has been presented for a second kinetically significant intermediate in the aromatic S(,RN)1 reaction with which nucleophiles can react. Having the requirements that this intermediate be both paramagnetic and a precursor to free aryl radical, its identity was discussed with respect to several possibilities: haloarene radical anion, exicted state aryl radical and excited state aryl radical/halide complex;Finally on the basis of these results, and those reported in the literature for both the aromatic and aliphatic S(,RN)1 reactions, several conclusions are reached regarding the requirements for the successful coupling of a radical with a nucleophile.