A series of anatase TiO2 nanowires (TiO2-NWs) and Ag-modified TiO2 nanowires (TiO2@Ag-NWs) film electrodes with hierarchical 3D nano-network structure are successfully synthesized via a facile hydrothermal process followed by the traditional silver mirror reaction. Successful modification of silver nanoparticles onto the TiO2-NWs surface is confirmed by X-ray diffraction, scanning electron microscope, transmission electron microscopy with energy-dispersive X-ray analysis, and inductively coupled plasma technique. The electrochemical performances of the TiO2-NWs and TiO2@Ag-NWs film electrodes are also investigated in this work. Compared with the pristine TiO2-NWs, the TiO2@Ag-NWs nanomaterial exhibits a higher rate capability and better reversibility. At charge/discharge rates of 50, 100, 200, 400, 800, 1600 and 3350mA/g, the discharge capacities of the TiO2@Ag-NWs electrodes are 237, 219, 198, 179, 159, 139 and 120mAh/g, respectively. After 120 cycles at 200mA/g, its capacity retention was as high as 99.1% with little capacity fading.