In this work, VO43- substitution for PO43- in the Nasicon structured Li3Sc2(PO4)(3) was used to enhance its ionic conductivity. The VO43- substitution resulted in a homogeneous compound Li3Sc2(PO4)(3-x)(VO4)(x) within a wide composition range of 0 <= x <= 1.2; further increase in x led to precipitation of the crystalline phases VPO5, V(PO3)(3) and ScVO4. Electrical conductivity of the VO43--substituted samples increased with the VO43- content, and the sample with x=1.5 exhibited the highest conductivity (8.41 x 10(-3) S m(-1)) at room temperature and the lowest activation energy (39.65 kJ mol(-1)). The obtained conductivity was two orders of magnitude higher than that of the non-substituted sample and nine times higher than those of the Zr4+ and SiO44--substituted compounds. The present study demonstrates that the VO43- anion substitution for PO43- is a promising technique to improve ionic conductivity of the Nasicon compound. (C) 2015 Elsevier Ltd. All rights reserved.