The new combined methodology for quantitative description of texture, structure and other microstructural parameters of thin layers using X-ray diffraction is presented and applied to the case of a ferroelectric thin film of Pb0.76Ca0.24TiO3 on a Pt/TiO2/SiO2/Si substrate. The approach allows the quantitative texture analysis of the ferroelectric thin film and the Pt electrode, refining simultaneously their structure, layers thickness, mean crystallite size and microstrain state. The layer thickness determination is estimated by the refinement of the thicknesses inserted in the absorption and volumic correction factors. The powerfulness of this methodology is discussed and compared with other approaches.