Silicon nanowires (NWs) have been reported as a promising anode that demonstrated high capacity without pulverization during cycling, however, they present some technical issues that remain to be solved. The high aspect ratio of the NWs and their small contact areas with the current collector cause high electrical resistance, which results in inefficient electron transport. The nano-size interface between a NW and the substrate experiences high shear stress during lithiation, causing the wire to separate from the current collector. In addition, most reported methods for producing silicon NWs involve high-temperature processing and require catalysts that later become contaminants. This study developed a new self-aligned Cu–Si core–shell NW array using a low-temperature, catalyst-free process to address the issues described. The silicon shell is amorphous as synthesized and accommodates Li-ions without phase transformation. The copper core functions as a built-in current collector to provide very short (nm) electron transport pathways as well as backbone to improve mechanical strength. Initial electrochemical evaluation has demonstrated good capacity retention and high Coulombic efficiency for this new anode material in a half-cell configuration. No wire fracture or core–shell separation was observed after cycling. However, electrolyte decomposition products largely covered the top surface of the NW array, restricting electrolyte access and causing capacity reduction at high charging rates.