This work is devoted to an “old” defect and its annealing characteristics, namely the divacancy centre in silicon. Infrared spectroscopy is applied to study the annealing kinetics of divacancy-related absorption peaks in electron-irradiated Czochralski-grown samples doped with boron. In all specimens the kinetics show an exponential decay (first-order process) and a model taking into account both diffusion and dissociation as annihilation mechanisms gives excellent quantitative agreement with the experimental results. Activation energy values extracted for diffusion and dissociation are 1.28 eV and 1.71 eV, respectively. In highly boron doped samples (0.1 °Cm), a strong dependence of the absorption bands on the Fermi-level position is observed during annealing below ∼ 200°C and concurrently, a change of the divacancy charge state from neutral to singly positive takes place.