Micro-nanostructured　electrode　materials　are　characterized　by　excellent　performance　in　various　secondary　batteries.　In　this　study,　a　facile　and　green　hydrothermal　method　was　developed　to　prepare　amorphous　vanadium-based　microspheres　on　a　large　scale.　Hollow　V2O5　microspheres　were　achieved,　with　controllable　size,　after　the　calcination　of　amorphous　vanadium-based　microspheres　and　were　used　as　cathode　materials　for　lithium-ion　batteries.　As　the　quantity　of　V2O5　microspheres　increased,　the　electrode　performance　improved,　which　was　ascribed　to　the　smaller　charge　transfer　impedance.　The　discharge　capacity　of　hollow　V2O5　microspheres　could　be　up　to　196.4　mAhg−1　at　a　current　density　of　50　mAg−1　between　2.0　and　3.5　V　voltage　limits.　This　sheds　light　on　the　synthesis　and　application　of　spherical　electrode　materials　for　energy　storage.