The gas-phase reaction of Cl atoms with benzene has been studied using both experimental and computational methods. The bulk of the kinetic data were obtained using steady-state photolysis of mixtures containing Cl2, C6H6, and a reference compound in 120−700 Torr of N2 diluent at 296 K. Reaction of Cl atoms with C6H6 proceeds via two pathways; (a) H-atom abstraction and (b) adduct formation. At 296 K the rate constant for the abstraction channel is k1a = (1.3 ± 1.0) × 10-16 cm3 molecule-1 s-1. Phenyl radicals produced via H-atom abstraction from C6H6 react with Cl2 to give chlorobenzene. The main fate of the C6H6−Cl adduct is decomposition to reform C6H6 and Cl atoms. A small fraction of the C6H6−Cl adduct undergoes reaction with Cl atoms via a mechanism which does not lead to the production of C6H5Cl, or the reformation of C6H6. As the steady-state Cl atom concentration is increased, the fraction of the C6H6−Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate c...