The paper presents the results of two-layer thin ferroelectric PZT films studies with a change in the lead content over the thickness of the films, obtained by RF magnetron deposition at various pressures of the working gas mixture. The microstructure and elemental composition were investigated by scanning electron microscopy and electron probe X-ray spectral microanalysis. It is shown that the elemental composition and dielectric properties depend on the sequence of layers deposition. The results obtained make it possible to characterize the physical mechanism of self-polarization formation in thin PZT films.