Ultrathin V2O5 nanosheets were successfully prepared through supercritical solvothermal reaction followed by annealing treatment. The formation of ultrathin nanosheets is owing to Ostwald ripening and the effect of supercritical fluids. As cathode material for lithium batteries, the ultrathin V2O5 nanosheets exhibit a capacity of 108 mA h g(-1) at a high rate of up to 10 C at 2.4-4 V and excellent cyclability with little capacity loss after 200 cycles. The enhanced rate performance is attributed to the shortened diffusion distance and the increased electrode-electrolyte contact area of the ultrathin nanosheet structure. It is also demonstrated that the supercritical solvothermal method is effective and facile to scalably synthesize ultrathin nanomaterials for lithium batteries.