Local vibrational mode (LVM) spectroscopy is used to explore the effect of high hydrostatic pressure (HP) on the formation of small oxygen-related clusters (dimers, trimers, thermal donors, and C–O complexes) at 450°C and 650°C in Cz–Si crystals with different impurity content and prehistory. It is found, in agreement with previous studies, that HP enhances the oxygen clustering in Cz–Si at elevated temperatures. The effect of HP is related mainly to enhancement in the diffusivity of single oxygen atoms and small oxygen aggregates. HP does not noticeably increase the binding energies of the most simple oxygen related complexes like O2i, CsOni. The biggest HP effect on the thermal double donor (TDDs) generation is revealed in hydrogenated samples. Heat-treatment of such samples at 450°C under HP results in extremely high TDD introduction rates as well as in a strong increase in the concentration of the first TDD species.