We present a study of the role of boron and oxygen in the chemistry of deuterium retention in boronized ATJ graphite irradiated by the extreme environment of a tokamak deuterium plasma. The experimental results were obtained by the first XPS measurements inside the plasma chamber of the National Spherical Torus Experiment Upgrade, between the plasma exposures. The subtle interplay of boron, carbon, oxygen and deuterium chemistry is explained by reactive molecular dynamics simulations, verified by quantum–classical molecular dynamics and successfully compared to the measured data. The calculations deciphered the roles of oxygen and boron for the deuterium retention and predict deuterium uptake into a boronized carbon surface close in value to that previously predicted for a lithiated and oxidized carbon surface.