La‐Sr‐Co‐O/Pb‐La‐Zr‐Ti‐O/La‐Sr‐Co‐O thin‐film capacitors have been grown in various oxygen ambients by pulsed laser deposition. As the oxygen ambient became more reducing, the capacitors developed more voltage asymmetry in hysteresis loops and a more preferred polarization state directed towards the top electrode. PLZT capacitors cooled in a fully oxidizing atmosphere (i.e., 1 atm oxygen pressure) exhibited nominally symmetric hysteresis loops and also showed little imprint both with and without fully saturating bias fields. We find that ambient oxygen pressure is an important process parameter and the imprint behavior is closely related with ambient oxygen induced effects such as oxygen vacancies, its related defect‐dipole complexes and trapping of free charges. The different imprint behavior under negative and positive bias also suggests that the dipolar‐defect complexes tend to cause imprint in PLZT capacitors.