Abstract The 0.9Pb(Sc0.5Ta0.5)O3-0.1%PbTiO3/0.55Pb(Sc0.5Ta0.5)O3-0.45%PbTiO3 (PSTT10/PSTT45) multilayer thin films were deposited on SiO2/Si(100) substrates by radio frequency magnetron sputtering technique with a LaNiO3 buffer layer, and the films were subsequently annealed by a two-steps rapid thermal approach. With this method, the films possess a highly (100) orientation, which is attributed to the introduction of LaNiO3 buffer layer. Enhanced dielectric and ferroelectric properties were observed in the multilayer thin films with low anneal temperatures of 700–750°C. Typically, the films annealed at 700°C have a high dielectric constant of ∼698.5 and a low dielectric loss of 0.054. In addition, such a thin film also exhibits a large remnant polarization of 5.45μC/cm2. The crystallization, the percentage pyrochlore and the loss of Pb are considered to play an important role on electric properties of the films.