A　simple　and　versatile　method　was　developed　to　prepare　hollow　Paramontroseite　VO2　microspheres.　Hollow　VO2　microspheres　were　formed　via　an　Ostwald　ripening　mechanism.　The　morphology,　crystalline　structure　and　electrochemical　performance　were　systematically　studied.　It　was　found　that　hollow　Paramontroseite　VO2　microspheres　can　be　used　as　stable　anode　and　cathode　materials　for　lithium　ion　batteries　with　acceptable　rate　cycling　performance.　In　addition,　the　discharge　capacities　of　hollow　paramontroseite　VO2　microsphere-based　negative　electrodes　were　found　to　reach　384.2　mAhg(-1)　at　a　current　density　of　750　mAg(-1).　A　discharge　capacity　of　195.6　mAg(-1)　was　achieved　when　the　microspheres　were　used　as　a　cathode　material　for　lithium-ion　batteries　at　a　current　density　of　20　mAg(-1).　Vanadium　based　dual　electrode　materials　are　seldom　reported　in　the　literature.