The formation of the divacancy-oxygen centre (V(2)O) in p-type Czochralski-grown silicon has been investigated by means of deep level transient spectroscopy (DLTS). The donor state (+/0) of V(2)O is located at ~E(v) + 0.23 eV (E(v) denotes the valence band edge) and emerges during heat treatment above 200 °C at the expense of the divacancy centre (V(2)). A concurrent transition takes place between the single-acceptor states of V(2) and V(2)O, as unveiled by the injection of electrons through optical excitation during the trap filling sequence of the DLTS measurements. Further, a defect with an energy level at ~E(v) + 0.09 eV evolves in close correlation with the growth of V(2)O but at a factor of ~5-6 lower in concentration. In the literature, the E(v) + 0.09 eV level has previously been attributed to a double-donor state of V(2)O but this assignment can be ruled out by the present data favouring a complex formed between migrating V(2) centres and a competing interstitial oxygen trap. In addition, a level at ~E(v) + 0.24 eV occurs also during the heat treatment above 200 °C and is tentatively assigned to the trivacancy-oxygen centre (V(3)O).