The influence of the post-deposition cooling speed on the domain formation process of PbTiO 3 films was investigated using MOCVD equipment combined with in-situ Raman spectroscopy. The accumulation and relaxation of strain during the post-deposition cooling process is responsible for the domain structure. The Curie temperature for fast cooling is lower than that for slow cooling. Additionally, the residual strain with fast cooling is smaller than that with slow cooling. These observations suggest that the volume fraction of the c-domain is larger for fast cooling and that the atmospheric conditions during the first post-deposition cooling process may control the domain structure.