The uniform, dense, and crack-free PbZr0.4Ti0.6O3/PbZr0.5Ti0.5O3 bilayer with (100)-preferred crystal orientation and a single perovskite phase was fabricated on LaNiO3-coated Si substrate by using chemical solution deposition. The bilayer exhibits excellent ferroelectric properties, remnant polarization of 64μC/cm2 and coercive field of 43.6kV/cm. The prism-film coupling measurement indicates that four transverse electric modes can be excited in the system of Si/LaNiO3/PbZr0.5Ti0.5O3/PbZr0.4Ti0.6O3 and the light can be effectively confined to propagate in the guiding-layer. The refractive index and thickness for each film were obtained by solving the mode eigen-equation of the waveguide.