In　the　present　work,　we　focus　on　the　development　of　hierarchical　MoO2-C　hollow　spheres　with　large　reversible　capacity　and　high　rate　capability　in　lithium　ion　batteries.　The　hierarchical　MoO2-C　hollow　spheres　assembled　by　MoO2　nanoparticles　were　initially　synthesized　successfully　through　ethanol　thermal　reduction　method,　followed　by　annealing　process.　Due　to　the　synergistic　effect　between　the　assembled　hierarchical　hollow　structure　and　the　carbon　coating,　the　sample　exhibited　excellent　electrochemical　properties　as　anode　material　for　lithium-ion　batteries.　For　example,　a　large　reversible　capacity　of　763　mA　h　g−1　was　obtained　after　50　cycles　at　a　current　density　of　0.2　A　g−1.　In　addition,　a　large　reversible　capacity　of　573　mA　h　g−1　can　be　remained　when　the　current　density　reached　at　the　high　current　density　of　2　A　g−1,　indicating　that　the　hierarchical　MoO2-C　hollow　spheres　electrode　possess　an　outstanding　rate　performance.　©　The　Royal　Society　of　Chemistry.