In this research, VO43 substitution was used to improve electrochemical properties of the Nasicon Li3Fe2( PO4)(3) cathode material. The VO43 substitution resulted in formation of a homogeneous compound Li3Fe2( PO4)(3-x)(VO4)(x) in a composition range of x <= 0.45; further introduction of VO43 led to precipitation of some other phases. It was shown that the VO43 substituted samples presented discharging capacity higher than that of bare non-substituted Nasicon and the reported Ti4+ and Mn2+ doped ones. The Li3Fe2( PO4)(2.55)(VO4)(0.45) material exhibited excellent cycling stability and rate capability, and retained a capacity of 91.8 mAhg (1) after 60 cycles at 2C charge-dischargerate. This value is one of the highest reported to date for the Li3Fe2( PO4)(3) compound, and was about 48% higher than that of the latter. The electrochemical performance enhancements for the VO43 substituted samples were attributed to the reduction of charge transfer resistance, increase of electrical conductivity, and fast lithium ion diffusion behavior. Hence, the obtained results proved that the VO43 anion substitution for PO43 is a powerful technique to improve the electrochemical performance of the studied Nasicon compound. (C) 2016 Elsevier Ltd. All rights reserved.