The chemical dynamics of the combustion-relevant reaction of phenyl radicals with molecular oxygen were investigated in a crossed beam reaction at a collision energy of 107 kJ mol(-1). Under these conditions, the formation of the phenoxy radical (C6H5O) plus ground state atomic oxygen was observed; no atomic hydrogen exchange pathway was opened. The reaction dynamics of the phenoxy radical channel were found to be direct, involved a stripping-like reaction mechanism, and were initiated by a radical-radical recombination of phenyl plus molecular oxygen forming a short lived phenylperoxy radical (C6H5O2). The latter decomposed to the phenoxy radical plus atomic oxygen; the overall reaction was exoergic by about 38 +/- 15 kJ mol(-1). Published by Elsevier B.V.