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Rechargeable lithium ion batteries (LIBs) have been widely used in portable electronics and become the prime candidate to power electric vehicles.1 Over the past decades,vanadium oxides and vanadates have been extensively studied as cathode materials for LIBs due to their high capacities,low cost and abundant resources.2-4 Here,Na0.33V2O5 nanosheet-graphene hybrids were successfully fabricated for the first time.The strategy mainly involves a novel hydrothermal method and a freeze-drying technique.The as-obtained Na0.33V2O5 nanosheets are uniform with a thickness of about 30 nm.The Na0.33V2O5 nanosheet-graphene hybrids show special sandwich-like nanostructures with high discharge capacity,good cycling stability and superior rate performance as cathodes for lithium storage.