Abstract X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and scanning electron microscopy experiments were carried out in the (Pb0.88Eu0.08)TiO3 ferroelectric compound with a perovskite type structure. Qualitative EXAFS analysis has shown that Eu3+ ions substitute to Pb2+ and Ti4+ ions at A and B sites of the ABO3 structure, respectively. The XRD pattern refinement was consistent with the Eu3+ substitution at both A and B sites, which provides the formation of donor and acceptor-type defects. The shape of the observed X-ray lines profiles has shown features, which are known for this kind of ferroelectric material to be typical of the ferroelectric domains microstructure. A phenomenological model has been used for fitting the diffraction profiles by the Rietveld method.