Ferroelectric thin films were deposited on the Si(100) substrate at for 2 hrs by metalorganic chemical vapor deposition (MOCVD) and post-annealed at 850oC by rapid thermal process (RTP). Electrical properties and crystalline phases of thin films were investigated as a function of postannealing time. Single phase of hexagonal symmetry with c-axis preferred orientation was obtained from thin films post-annealed at for 5 min, while the c-axis preferred orientation was decreased with the increase of post-annealing time, and the thin films post-annealed at for 15 min showed the mixture phases of hexagonal and orthorhombic symmetry. P-E (Polarization-Electric field) hysteresis loop of ferroelectric thin films was observed only for the single phase of hexagonal symmetry, but that was not observed for the mixture phases of the hexagonal and orthorhombic symmetry, which was discussed with the bond valence of Mn ion of crystalline phase. Leakage current density was dependent on the microstructure of thin films as well as the change of valence of Mn ion.