The reliability factors of a Rietveld X-ray powder refinement of PbCrO{sub 3} could be improved by considering the lead ion in a multi-minimum potential displaced from its special position. These studies coupled to EDX analysis show a certain lead deficiency. Electron diffraction and high-resolution electron microscopy reveal that the microstructure of this material is a rather complex perovskite superstructure that presents a compositional modulation, within a microdomain distribution. The proposed supercell is {approx}a{sub p}x3a{sub p}x({approx}14-18)a{sub p}. - Graphical abstract: Model of the structure of PbCrO{sub 3} obtained by electron microscopy and diffraction.