The application Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy for the study of local structural environment of different ions in material is described. This technique is particularly useful for materials when parent compounds are doped with small amount of dopant impurities, because the local environment of individual atomic species can be determined. EXAFS results of Nb5+ doped alkaline earth ferates (BaFe1-x NbX O3 ) are illustrated as an example. These results show that the local environment of the dopant ion is different from that of the host atoms. This variation in local structure depends on the concentration of the dopant ion. The Fe-Obond lengths increase as the concentration of the dopant ion (Nb5+ ) is increased. However the Nb-O bond lengths do not vary significantly with the Nb5+ concentration, indicating that the dopant local environment is independent of its concentration. In the case of BaFe1-XNbXO3 a local structural change was observed around the Fe.