The Mg-doped Li3V2− x Mg x (PO4)3 (x =0.00, 0.01, 0.02, 0.05, 0.10, 0.20, 0.30, 0.33, 0.50, 1.00 and 1.33) compounds have been prepared by a sol–gel method in reducing atmosphere (70%Ar+30%H2) using citric acid as a chelating agent and a carbon source coated on the samples. The Mg-doped effects on the structural and electrochemical performance of Li3V2(PO4)3 are investigated by X-ray diffraction, galvanostatic, charge/discharge and four-point probe measurement method. The Li3V2− x Mg x (PO4)3 solid solution phase can exist stable in the composition range between x =0.00 and 0.27. The simple improve mechanism of the electrochemical performance for Mg-doped Li3V2− x Mg x (PO4)3 system is discussed too. In the Mg-doped Li3V2− x Mg x (PO4)3 system, at a lower charge/discharge rate (0.1C), the cycle performance has no much improvement with the increasing Mg doping content. However, at higher rates, there has an excited improvement in both cycle performance and rate capability due to the increase of electrical conductivity (more than one order of magnitude). At 5C charge/discharge rate, for the Li3V1.95Mg0.05(PO4)3 sample, the discharge capacities for the 1st and 100th cycle were 138.9 and 123.3mAhg−1. The discharge capacity retention reached to 89% (more than 51% for undoped Li3V2(PO4)3 system). More important is that, except for the first 15 cycles, the discharge capacities kept almost a constant. Based on the excellent electrochemical performance, Li3V1.95Mg0.05(PO4)3 will be a promising cathode material for rechargeable lithium-ion batteries.