Water radiolysis has been investigated by in situ and direct detection by using the scavenging method and 13-keV X-rays from ESRF synchrotron. By using a famous chemical system, concentrated hydrobromic acidic solutions over a range of concentrations (from 0.1 to 0.6 moledm−3), and real time absorption spectroscopy of Br3− around 266 nm, we aimed at evaluating the effect of 13-keV X-rays, below the ionization K-edge of Br, on the Br− oxidation yield value. The HO• scavenging time ranging in the picosecond scale is also taken into consideration going to the earliest initial yields. We have also observed the limit of use of N2O and air as saturation gas. The oxidation limitation also comes from the presence of H3O+ in abundance giving birth of competitive reactions. The determination of the dose rate delivered to the solution has been performed by using the Fricke dosimeter system by following absorbance at 304 nm. The dose rate was 18.5 Gys−1.