Ce atom is employed to partially substitute V site in Na3V2(PO4)3 (NVP) crystal structure to improve its bulk phase characteristic. The effect of Ce substitution on the crystal structure, morphology, electrochemical performance and kinetic property of NVP is investigated based on rational design and synthesis optimization. The results indicates that the moderate Ce substitution in the NVP crystal can effectively enhance the bulk phase electronic conductivity and Na+ mobility, which excludes the carbon coating effect for the first time. And Na3V1.96Ce0.04(PO4)3/C shows the best electrochemical performances among the Na3V2-xCex(PO4)3/C (x=0, 0.02, 0.04, 0.06 and 0.1) samples. It delivers a discharge capacity of 118mAhg−1 at 0.2C and more than 100mAhg−1 even at 40C, which is currently the highest level by metallic ion doping. After 100 cycles, the capacity retention of Na3V1.96Ce0.04(PO4)3/C keeps higher than 99% at 10C. The outstanding performance of the moderate Ce-doping sample is verified further by the electrochemical performance test of the samples with high mass loading, which is highly beneficial to industrial applications of Na3V2(PO4)3 cathode for high performance sodium ion batteries.