Co-doped Li3V2−x Co x (PO4)3/C (x =0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li3V2−x Co x (PO4)3/C (0≤ x ≤0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li3V2−x Co x (PO4)3. XPS studies also revealed that V4+ and V3+ ions were present in the Co2+-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x >0.10. Differential capacity curves of Li3V2−x Co x (PO4)3/C compounds showed that the voltage peaks associated with the extraction of three Li+ ions shifted to higher voltages with an increase in Co content, and when the Co2+-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li3V2(PO4)3 phase. For the Li3V1.85Co0.15(PO4)3/C compound, the initial capacity was 163.3mAh/g (109.4% of the initial capacity of the undoped Li3V2(PO4)3) and 73.4% capacity retention was observed after 50 cycles at a 0.1C charge/discharge rate. The doping of Co2+into V sites should be favorable for the structural stability of Li3V2−x Co x (PO4)3/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li+ extraction/insertion, thus resulting in the improvement of cell cycling ability.