Novel hierarchical Ru-doped Na3V2O2(PO4)2F hollow microspheres were synthesized via a low-temperature solvothermal method. The individual unique microspheres were formed from assembly of numerous nanoparticles with diameters of 20–30nm. When used as a cathode material for sodium-ion batteries (SIBs), the microspheres exhibited superior rate performance with a capacity of 72.6 mAh·g−1 at 10C. Furthermore, their rate performance could be significantly improved by coating them with a thin conductive RuO2 layer. For instance, high specific capacities of 102.5mAhg−1 and 44.9mAhg−1 were achieved at current rates of 20C and 100C, respectively. These materials exhibited impressive long-term cycling stability. A reversible capacity of approximately 55.0mAhg−1 was maintained even after 7500 charge/discharge cycles. Density functional theory (DFT) calculations increased our understanding of how H+ facilitates the formation of the hierarchical microsphere superstructure which is beneficial to achieve a good rate capability.