The combination of the quantitative texture analysis and Rietveld methods is used to study the preferential orientation of morphotropic phase boundary (MPB) Pb(Mg1/3Nb2/3)O3‐PbTiO3 ceramics obtained by homogeneous Templated Grain Growth. Their complex structure, with the coexistence of several polymorphs, and the presence of texture that is required to take advantage of their excellent piezoelectric properties, raise serious problems for a precise characterization of these materials. Conventional methods of texture analysis, although simple, are limited, and the information obtained, if not studied with care, may be misleading. The use of linear detectors and χ‐scan are more appropriate for the study of diffraction peaks with several contributions as it is the case for MPB compositions. This work shows the simultaneous determination of structural and texture parameters through the application of the so‐called combined method, already used for the analysis of similar problems in a range of polycrystalline materials, to this specific case.