Na(3)V(2-x)Fex(PO4)(3)/C (0 <= x <= 0.5) samples were prepared by a simple sol-gel method. X-ray diffraction patterns revealed high purity and crystalline phosphate indexed in the R-3c space group. On increasing the iron content, the cell volume increases due to the slightly higher radius of Fe3+. Cyclic voltammetry showed two signals at ca. 3.5 and 4.0 V, which evidence a linear dependence of potential on the level of substitution. The appearance of the short plateau at ca. 4.0 V is closely related to the higher iron substitution levels. The evaluation of XPS and Fe-57 Mossbauer spectra of charged and discharged electrodes allow ascribing the 4.0 V plateau to V4+/V5+ redox reaction and the extraction/insertion of extra sodium ions from octahedral M1 sites. Galvanostatic cycling showed capacity values as high as 115 mA h g(-1) for samples with x = 0.1, 0.2, 0.3 and exceptional cyclability. (C) The Author(s) 2015. Published by ECS.