Novel　hierarchical　Ru-doped　Na3V2O2(PO4)(2)F　hollow　microspheres　were　synthesized　via　a　low　-temperature　solvothermal　method.　The　individual　unique　microspheres　were　formed　from　assembly　of　numerous　nanoparticles　with　diameters　of　20-30　nm.　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　10　C.　Furthermore,　their　rate　performance-could　be-significantly　improved　by-coating　them-with　a　thin　conductive　RuO2　layer.　Fot　instance,　high　specific　capacities　of　102.5　mAh　g(-1)　and　44.9　mAh　g(-1)　were　achieved　at　current　rates　of　20　C　and　100　C,　respectively.　These　materials　exhibited　impressive　long-term　cycling　stability.　A　reversible　capacity　of　approximately　55.0　mAh　g(-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.