The electrical and magnetic properties of rare earth orthoferrites are strongly dependent upon the electronic structure of Fe cations. This study investigates the electronic structure of Fe as a function of composition in LaFe1-xNixO3 using Fe K-edge X-ray absorption spectroscopy at room temperature. Analysis of the Fe K-edge X-ray absorption spectra indicates the presence of Fe3+ and Fe4+ in LaFe1-xNixO3. The concentration of F4+ increases with increasing Ni content in LaFe1-xNixO3. Variations in the oxidation state of Fe have been correlated to those in the electrical and magnetic characteristics of LaFe1-xNixO3. (C) 2014 Elsevier B.V. All rights reserved.