The rate constant for the reaction of phenyl radical with hydrogen bromide has been measured with the cavity‐ring‐down method at six temperatures between 297 and 523 K. The Arrhenius expression for the H abstraction reaction can be effectively given by: (Formula Presented.) . The values of these parameters are similar to those for the H + HBr reaction, but are in sharp contrast to those for alkyl radical reactions. The gross difference between the alkyl radical reactions and the phenyl and H‐atom reactions could be rationalized in terms of the inductive effects of these radicals as measured by Taft's σ* (polar) constants. © 1993 John Wiley & Sons, Inc.