The modified polymeric precursor method (Pechini method) was successfully used for the preparation of epitaxial and polycrystalline ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) thin films. Films were deposited on LaNiO3 (LNO) – coated silicium (1 0 0) and platinum substrates (Pt (1 1 1)/Ti/SiO2/Si) by spin coating technique. LNO electrodes were also prepared by the Pechini method and treated under different thermal treatment conditions to obtain films with different structural and microstructural properties. Investigation of PZT microstructure was performed as a function of orientation and morphology of the bottom electrode, as well as of thermal treatment conditions. Grain size and morphology were analyzed by AFM, while the quality and orientation of PZT films were determined by GIXRD analysis. It has been found that the proposed thermal treatment on a hot plate, with slow heating rate and long annealing time, can result in the formation of epitaxial PZT films on Si and LNO-coated Si substrates.