The reaction mechanisms in the Si/Ta/Cu metallization system and their relation to the microstructure of thin films are discussed on the basis of experimental results and the assessment of the ternary Si–Ta–Cu phase diagram at 700 °C. With the help of sheet resistance measurements, Rutherford backscattering spectroscopy, x-ray diffraction, a scanning electron microscope, and a transmission electron microscope, the Ta barrier layer was observed to fail at temperatures above 650 °C due to the formation of TaSi2, the diffusion of Cu through the silicide layer, and the resulting formation of Cu3Si precipitates. However, in order for the TaSi2 phase to form first, the Ta diffusion barrier layer must be thick enough (e.g., 50–100 nm) to prevent Cu diffusion into the Si substrate up to the temperature of TaSi2 formation (∼650 °C). Independent of the Ta layer thickness, Cu3Si was present as large nodules, whereas the TaSi2 existed as a uniform layer. The resulting reaction structure was found to be in local equilibrium on the basis of the assessed Si–Ta–Cu phase diagram at 700 °C, and therefore no further reactions were expected. The role of oxygen was also found to be important in the reactions and it seems to have a strong effect on the thermal stability of the barrier layer.