Novel channel-structured 尾-Ag0.33V2O5 nanorods have been successfully synthesized via a simple hydrothermal process. The channels are along the axis of 尾-Ag0.33V2O5 nanorods and the channels are about 30 nm in width. As cathode material for lithium batteries, it exhibits higher specific discharge capacity and improved cyclic stability than other silver vanadium oxides. High initial specific discharge capacity of 288 mA h g鈭? can be obtained at 20 mA g鈭? in the voltage range of 2.0-3.6 V (vs. Li/Li+). A maximum high specific discharge capacity of 332 mA h g鈭? can be reached at 20 mA g鈭? within 1.5-4.0 V (vs. Li/Li+). The good electrochemical performances are ascribed to the novel channel-structure and good structural reversibility upon cycling.