The microstructure and electrical properties of P(VDF-TrFE)/Bi3.5Nd0.5Ti3O12 bi-layer composite ferroelectric thin films deposited on Pt/Ti/SiO2/Si using two successive spin coatings were investigated. It shows the pores in Bi3.5Nd0.5Ti3O12 (BNT) films were effectively suppressed by the presence of P(VDF-TrFE) copolymer films by SEM. The ferroelectric, leakage and dielectric properties of the thin films with different thickness ratio of P(VDF-TrFE) and BNT thin films were measured. With increasing the thickness of P(VDF-TrFE), the remnant polarization, coercive electric field, leakage current density and dielectric constant of thin films were all decreased (except pure P(VDF-TrFE) thin film). Results indicate that the key electrical properties were improved effectively by a little loss of the remnant polarization, which infers potential application in the filed of ferroelectric memory.