A novel two-step approach was developed to fabricate well-dispersed Na1.08V3O8nanosheets, which consist of ultra-thin monolayer sheets with a thickness of ca. 10 nm. The formation mechanism of nanosheets involves the fusion and conversion of nanorods. When used as a cathode material for Li-ion batteries, the nanosheets show superior rate capability, with discharge capacities of ca. 200.0, 131.3, 109.9, 94.2 and 72.5 mA h g−1 at 0.4, 10, 20, 30 and 50 C, respectively. Excellent cycling stability without considerable capacity loss over 200 cycles is observed at 600 and 1000 mA g−1. It is believed that the unique nanosheet morphology as well as its intrinsic structural features greatly facilitate the kinetics of Li-ion diffusion and excellent structure stability, thus resulting in superior electrochemical performance.