The reaction of (OH)-O-center dot with Br- has been reinvestigated by picosecond pulse radiolysis combined with streak camera absorption detection and the obtained spectro-kinetics data have been globally analyzed using Bayesian data analysis. For the first time, the absorption spectrum of the intermediate species BrOH center dot- has been determined. This species absorbs in the same spectral domain as Br-2(center dot-): the band maximum is roughly at the same wavelength (lambda(max) = 352 nm instead of 354 nm) but the extinction coefficient is smaller (epsilon(max) = 7800 +/- 400 dm(3) mol(-1) cm(-1) compared with 9600 +/- 300 dm(3) mol(-1) cm(-1)) and the band is broader (88 nm versus 76 nm). Quantum chemical calculations have also been performed and corroborate the experimental results. In contrast to Br-2(center dot-), the existence of several water-BrOH center dot- configuration leading to different transition energies may account for the broadening of the absorption spectrum in addition to the higher number of degrees of freedom.