Lead-free 0.5Ba(Zr0.2Ti0.8)O-3-0.5(Ba0.7Ca0.3)TiO3 (BZT BCT) and the La0.5Sr0.5CoO3 (LSCO) bottom electrode films were epitaxially grown onto the CeO2/Y0.15Zr0.85O1.93 (YSZ) buffered Si (001) substrates via pulsed laser deposition. The lattice alignments between CeO2/YSZ and BZT BCTILSCO showed a 450 twisted cube-on-cube epitaxial relationship, indicating a high crystallinity of the BZT BCT and LSCO films. The constituent elements in the BZT BCT/LSCO/CeO2/YSZ structure showed no distinct inter-diffusion between each layer. The BZT BCT epitaxial films showed a well saturation of the polarization electric field (P-E).