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BiFeO3 (BFO), Mn-doped-BFO (BFMO), Ti-doped-BFO (BFTO), and (Mn,Ti)-codoped-BFO (BFMTO) thin films are fabricated on the Pt/TiO2/SiO2/Si substrates via a sol–gel method combined with spin-coating and the subsequent layer-by-layer annealing technique. Compared with BFO film, the BFMTO film exhibits the lowest leakage current density ([Formula: see text][Formula: see text]A/cm2@290[Formula: see text]kV/cm). Notably, the polarization–electric field (P–E) loop of BFMTO film exhibits a positive displacement along the x-axis due to the existence of internal bias electric field, which is in agreement with the results of the PFM phase and amplitude curves. Especially, a very prominent inverse piezoelectric constant of [Formula: see text][Formula: see text]pm/V was obtained, which overcomes other related thin films. The internal bias electric field of BFMTO film can be caused by the different work functions of the thin film and the bottom electrode, accumulation of oxygen vacancies and the formation of defect dipoles. Besides, the internal bias electric field of BFMTO film has a good stability at the same electric field after experiencing the test cycle from low electric field to high electric field (400–1900[Formula: see text]kV/cm). These results indicate that self-polarized BFMTO film can be integrated to devices without additional polarization process, and have a wide range of application in microelectromechanical systems.