AbstractUniformly (111)‐oriented, multiply twinned SrRuO3‐covered platinum electrodes have been grown on YSZ(100) buffer layers on Si(100) substrates by a combination of r.f. sputtering and pulsed laser deposition (PLD). They provide a smooth and plane substrate surface for the growth of multiply twinned, uniformly (104)‐oriented ferroelectric Bi3.25La0.75Ti3O12 (BLT) and Bi3.54Nd0.46Ti3O12 (BNT) thin films grown by PLD at an optimum substrate temperature of 750 °C. Microstructure, morphology and crystallographic orientation of the SrRuO3/Pt electrodes and the BLT and BNT films are characterized by XRD, AFM, TEM, and SAED. In spite of the multiply twinned structure, the entire ferroelectric film has a uniform component P⊥ of the polarization vector perpendicular to the film plane. The (104)‐oriented BLT and BNT films on electroded Si(100) are shown to have good ferroelectric properties (remanent polarization, coercive field, fatigue resistance) and are thus suitable for applications in silicon‐based technologies. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)