Rational assembly of unique complex nanostructures is one of the facile techniques to improve the electrochemical performance of electrode materials. Here, a substrate-assisted hydrothermal method was designed and applied in synthesizing moundlily like radial β-AgVO(3) nanowire clusters. Gravitation and F(-) ions have been demonstrated to play important roles in the growth of β-AgVO(3) nanowires (NWs) on substrates. The results of cyclic voltammetry (CV) measurement and X-ray diffraction (XRD) characterization proved the phase transformation from β-AgVO(3) to Ag(1.92)V(4)O(11) during the redox reaction. Further electrochemical investigation showed that the moundlily like β-AgVO(3) nanowire cathode has a high discharge capacity and excellent cycling performance, mainly due to the reduced self-aggregation. The capacity fading per cycle from 3rd to 51st is 0.17% under the current density of 500 mA/g, which is much better than 1.46% under that of 20 mA/g. This phenomenon may be related to the Li(+) diffusion and related kinetics of the electrode. This method is shown to be an effective and facile technique for improving the electrochemical performance for applications in rechargeable Li batteries or Li ion batteries.