In　the　present　study,　for　the　first　time,　hierarchically　structural　microflowers　composed　of　Fe-doped　GeO2　nanosheets　have　been　synthesized　via　a　facile　solvothermal　route.　It　has　been　found　that　Fe3+　was　not　only　a　structure-directing　agent,　facilitating　the　formation　of　hierarchical　structure　by　a　self-assembly　process,　but　also　used　for　in　situ　doping　of　GeO2.　As　a　result,　an　anode　with　a　hierarchical　structure　shortened　the　diffusion　distance　of　Li+　and　hierarchically　buffer　volume　expansion.　Simultaneously,　Fe-GeO2　with　oxygen　vacancies　and　narrower　bandgaps　could　provide　more　active　sites　for　Li　insertion　and　improve　the　electrical　conductivity,　respectively.　Consequently,　Fe-doped　GeO2　delivered　an　ultra-long　cycling　stability　of　866　mA　h　g-1　even　after　1000　cycles　at　a　current　density　as　high　as　1　A　g-1.　It　is　unexpectedly　found　that　Fe　also　played　a　role　of　catalyst　for　reversible　utilization　of　partial　Li2O.　©　2019　The　Royal　Society　of　Chemistry.