An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine ( reaction 1) has been performed by using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297-766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A nonlinear least-squares fit with two floating parameters of the temperature-dependent k(1)(T) data set using an equation of the form k(1)(T) = AT(n) yields the recommended expression k(1)(T) (1.85 x 10(-9)) T-0.66 cm(3) molecule(-1) s(-1) for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated with use of quantum chemistry methods. The reaction proceeds through formation of a weakly bound (OHBr2)-Br-... complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled by using the RRKM method on the basis of the calculated PES.