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A series of Cr-doped Li
3
V
2-x
Cr
x
(PO
4
)
3
/C (x = 0.00, 0.10, 0.15, 0.20) composites was synthesized using Sol-gel method. The influence of Cr doping on the structure, morphology and electrochemical performance of Li
3
V
2
(PO
4
)
3
/C were studied. The X-ray diffraction patterns indicate that all of the samples are consistent with those of monoclinic Li
3
V
2
(PO
4
)
3
, indicating that Cr
3+
can be successfully doped into the lattice of Li
3
V
2
(PO
4
)
3
. Scanning electron microscopy, transmission electron microscopy mages revealed the morphology and the uniform distribution of Cr in the samples. In the potential range of 3.0-4.3 V, the Li
3
V
1.9
Cr
0.1
(PO
4
)
3
/C composite exhibited the highest discharge capacity of 125.1 mAh/g at 0.1 C, while the Li
3
V
1.8
Cr
0.2
(PO
4
)
3
/C performed a capacity of 95.8 mAhg
−1
with a high capacity retention ratio of 91.6% after 40 circles, which is still lower than the capacity of the Li
3
V
1.9
Cr
0.1
(PO
4
)
3
/C. Based on the excellent electrochemical performance, Li
3
V
1.9
Cr
0.1
(PO
4
)
3
/C will be a promising cathode material for rechargeable lithium-ion batteries.