Multilayer thick films ($4 mm) with compositional PbZr 0.3 Ti 0.7 O 3 /LaNiO 3 layers and one-layer PZT thick films were prepared on the silicon substrate by radio-frequency magnetron sputtering. PbZr 0.3 Ti 0.7 O 3 /LaNiO 3 multilayer thick film are characterized by highly preferential (100)-oriented growth and columnar microstructure due to alternately introducing LaNiO 3 seeding layers. The effects of LaNiO 3 layers on microstructure and electrical properties of PbZr 0.3 Ti 0.7 O 3 thick films were investigated in detail. The results show that both PZT and PbZr 0.3 Ti 0.7 O 3 /LaNiO 3 multilayer thick film were pure perovskite crystalline phase.The PbZr 0.3 Ti 0.7 O 3 film texture was dense and well adhered on the LaNiO 3 layer. PbZr 0.3 Ti 0.7 O 3 /LaNiO 3 multilayer thick film possessed obvious enhanced dielectric properties compared with PZT thick film: e r $2450 (10 kHz) and tand $0.02 (10 kHz). Rayleigh law was used to analysis the behavior of the enhanced dielectric properties and the pinched-shaped polarization-electric field hysteresis loops. The larger Rayleigh parameter, a $51.1408 cm kV À1 (1 kHz) indicates the larger extrinsic contribution to permittivity and strong domainwall-defect charge interaction. The leakage current behaviors of the multilayer thick film were also investigated in detail.ß 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1 Introduction With the development of siliconbased microelectromechanical systems (MEMS) technology, ferroelectric/piezoelectric thick films (1-100 mm) are a research hotspot from the viewpoint of their combining the advantages of bulk materials and thin films with high sensitivity, wide frequency range, good mechanical properties, and good compatibility with CMOS devices. PbZr x Ti 1Àx O 3 (PZT)-based thick films possess high reliabilities in applications of high-sensitivity sensors and pyroelectric infrared detectors. In addition, sensors and detectors based on PZT thick film can work in a broader working frequency range compared to those based on PZT thin films since they have higher dielectric constant, piezoelectric coefficient, and pyroelectric coefficient [1][2][3][4]. There are a variety of methods to prepare PZT thick films on silicon substrates, such as screen printing [5,6], sol-gel techniques [7], aerosol deposition [8], and magnetron sputtering [9]. Among them, the PZT thick films prepared by the first three processes need to be heat treated at high temperature (!850 8C), which may cause some issues such as cracks and voids. In contrast, the PZT thick films