A peony-like Ag/Ag0.68V2O5 hybrid assembled from nanosheets with the thickness of 40 nm was synthesized through a one-pot hydrothermal approach from vanadium pentoxide (V2O5), oxalic acid (H2C2O4), and silver nitrate (AgNO3) at 180 °C for 24 h. The hybrid exhibits high performance as both anode and cathode materials for rechargeable lithium batteries. Electrochemical measurements revealed that the as-prepared Ag/Ag0.68V2O5 hybrid displayed excellent cycling stability, especially as an anode material. The resulting anode retains 100% of the initial capacity after 1000 cycles under a current density of 400 mA g(-1). This phenomenon may be attributed to electron conductivity improvement by the existence of metallic silver in the hybrid in addition to the convenient access to lithium ion ingress/egress because of its unique structure.