Abstract Allying epitaxial strain and synthesis conditions allows for the introduction of specific point defects in perovskite oxide films. In ferroelectric films, such defects lead to essential polar and electronic properties, which can enable advanced applications. Here, to elucidate the nature of the defects, optical constants are investigated in the spectral range of 0.7–8.8 eV in epitaxial ferroelectric BaTiO₃ films, which are synthesized under different conditions. It is demonstrated that oxygen-vacancy-related defects are responsible for a peculiar transition below the bandgap at ∼2.7–2.9 eV and significant blueshifts of ∼0.3–0.4 eV of the gap and the main interband transitions. These observations suggest that the defects are dipolar complexes comprising titanium cations and oxygen vacancies (Ti³⁺–Vₒ).