The phase composition and specific features of the microstructures of layers in the Pb(Zr0.52Ti0.48)O3–LaNiO3–Si and Pb(Zr0.52Ti0.48)O3–LaNiO3–SiOx–Si compositions grown by chemical vapor deposition from solutions have been investigated by high-resolution transmission electron microscopy, electron diffraction, and energy-dispersive analysis. The influence of the structure of the lower LaNiO3 electrode on the structure and properties of ferroelectric lead zirconate titanate films with a perovskite structure is studied. It is shown that the misoriented porous polycrystalline structure of the lower electrode leads to violation of the columnarity of perovskite grains. The electrical parameters are slightly deteriorated in comparison with a conventional platinum electrode. The structures of the thin films with a silicate sublayer under the LaNiO3 electrode and without it are compared.