Currently, the poor intrinsic electronic and ionic conductivity significantly limits the further development of Na3V2(PO4)3 (NVP). In this paper, a feasible improvement strategy is proposed, which uses the sol-gel method to doped Lu3+ into Na3V2(PO4)3. According to the rietveld XRD occupancy refinement, the introduced Lu element occupies the Na1 site, which hardly affects the reversible de-intercalation of the two Na+ at Na2 site, behaving no side effects on the reversible capacity properties of the modified material. Besides, due to the smaller ionic radius of Lu3+ than that of Na+ (86.1 Å vs. 102 Å), Lu3+ substitution can increase the intercellular space within the crystal bulk to accelerate ionic migration and improve the ionic conductivity. Meanwhile, hypervalent and multicharged Lu3+ at Na1 site can cause the slight lattice distortions to induce more active sites for the storage of Na+, favorably increasing the reversible capacity. Furthermore, post-cycling XRD/SEM/XPS measurements demonstrate the significantly improved structural stability of NVP/C@Lu-1 % sample. Before and after cycling XPS spectra verify the stable existence of newly generated LuO band at 199.12 eV, which plays the role of an anchoring column to connect the crystal construction between lattice planes, and reduces the lattice strain to enhance the structure. According to the comparison of V2p XPS spectra before and after cycling, the peak location tends to move lower binding energy after introducing Lu3+ at Na1 site, indicating that NVP/C@Lu-1 % possesses a more stabilized framework. Overall, the optimized NVP/C@Lu-1 % submits an astonishing value of 123.9 mAh g−1 at 0.1C. Even at 7, 30, and 80C, it can release capacities of 97.1, 79.6 and 75.5 mAh g−1, and after 2000, 7500, and 8000 cycles, the capacities still keep 90.5, 73.2 and 68.3 mAh g−1 with retention of 93 %, 92 %, and 90.5 %.