To reveal the complete performance of intrinsic ferroelectriciy-related properties in single crystalline bismuth-layer-structured displacive ferroelectrics in film form on Si, the crucial roles of both orientation control technology by lattice matching from the atomic arrangement of substrate layer and configuration of the volume fraction of 90°-domain during cooling process were demonstrated. 1.2 μm-thick and Pr3+-substituted Bi4-xPrxTi3O12 (BPT, x =0.0, 0.3, 0.5, 0.7) films were grown on Ir(111)/Ti/SiO2/Si(001) substrates by chemical solution deposition (CSD) method with preferred orientation along the major component of P
vector. BPT film of x =0.3 exhibited superb ferroelectric properties of remanent polarization 2P
=92 μC/cm2, saturation polarization P
sat=50 μC/cm2, and coercive field 2E
=184 kV/cm. The film also showed uniform piezoelectric response with an effective piezoelectric coefficient of AFM-d
33=36 pm/V. During the decomposition of precursor solutions, IrO2 layers were formed at the surface of Ir layers and promoted a/b-axes orientation. During the cooling process after grain growth, in addition, the differential thermal expansion and residual strain between film and substrate introduced bidirectional lateral stress into BPT film and might eliminate the 90°-domain walls dividing a-and b-domains through the relaxation by domain formation at the Curie temperature T
. Consequently the polar-axis orientation was distinctively grown along the film normal and the conjugate non-polar-axis was grown in-plane.