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Abstract Deterministic control of the intrinsic polarization state of ferroelectric thin films is essential for device applications. Independently of the well‐established role of electrostatic boundary conditions and epitaxial strain, the importance of growth temperature as a tool to stabilize a target polarization state during thin film growth is shown here. Full control of the intrinsic polarization orientation of PbTiO₃thin films is demonstrated—from monodomain up, through polydomain, to monodomain down as imaged by piezoresponse force microscopy—using changes in the film growth temperature. X‐ray diffraction and scanning transmission electron microscopy reveal a variation ofc‐axis related to out‐of‐plane strain gradients. These measurements, supported by Ginzburg–Landau–Devonshire free energy calculations and Rutherford backscattering spectroscopy, point to a defect mediated polarization gradient initiated by a temperature dependent effective built‐in field during growth, allowing polarization control not only under specific growth conditions, but ex‐situ, for subsequent processing and device applications.