In this paper, we report on 4.5µm piezoelectric Pb(Zr0.52Ti0.48)O3 (PZT) thick films deposited on flexible stainless steel (SS) foils with LaNiO3 (LNO) buffer layers using a ceramic powder/sol–gel solution modified composite method. The polycrystalline thick films show a hysteresis loop at an applied electric field of 900 kV cm−1 with remanent polarization and coercive electric field values of 27µC cm−2 and 85 kV cm−1, respectively. At 1 kHz, the dielectric constant is 653 and the dielectric loss is 0.052. The leakage current density of the film is lower than 1.55 × 10−5 Acm−2 over the range of 0 to ±150V. The conduction current shows ohmic behaviour at a low electric field and space-charge-limited current characteristics at a high electric field.