PbFe1/2Nb1/2O3 (PFN) and BaFe1/2Nb1/2O3 (BFN) are perovskite oxides, combining ferroelectric and magnetic properties. Both of the compounds exhibit very high values of dielectric permittivity which make them attractive for application in multilayer ceramic capacitors. PFN. has been proved to be a disordered ferroelectric with Tc of about 110 °C, however the origin of the giant dielectric response in BFN is still under discussion, since it can be attributed not only to ferroelectric relaxor nature of BFN, but also to the oxygen defect induced dielectric anomaly. In order to get information on the local atomic structure of these compounds and their solid solutions we have performed XAFS study of number of samples with general formula PbxBa1-xFe1/2Nb1/2O3 (x=0, 0.1,0.2,0.3,1). The Fe K-edge EXAFS spectra have been recorded in the transmission mode at the beamline "Structural Materials Science" of the Kurchatov Center for Synchrotron Radiation and Nanotechnology (KCSRNT, Moscow, Russia). Fourier transformation of the k2-weighted EXAFS functions has been made over the range of 2.8–12.0 Å–1. Interatomic distances have been found by the non-linear fit of theoretical spectra to experimental ones. Fe2O3 has been used as a reference compound. For all the examined compounds the best fits were achieved assuming three short and three long Fe- O distances, indicating rhombohedral distortion of the Fe local environment, originated from Fe displacement off the center of oxygen octahedron. In PFN the results of the fit were very close to those of Fe2O3, indicating rhombohedral distortion. For BFN Fe local environment has been also successfully fitted within 2-shell model, however Fe-O distances appeared to be much longer than those in PFN. Basing on the results of the fit and assuming rhombohedral distortion, the displacements of the Fe ions from the centers of their octahedra for both PFN and BFN are estimated to be about 0.12 Å. It shows that both compounds possess quite substantial local dipole moments which may give rise to their dielectric properties. BFN demonstrates more symmetric Fe environment comparative to PFN. All changes of the spectra over the compositional range are gradual and independent of the macroscopic symmetry.