Here, we report on the simple, catalyst-free preparation and application of carbon nanotube-silicon core-shell composite anodes on stainless steel. The stainless steel mesh structure acts as a self-catalyzing agent for the plasma-enhanced chemical vapor deposition (PECVD) growth of vertically aligned, dense, multiwalled carbon nanotube arrays. The carbon nanotube array then serves as a bed for silicon deposition by the decomposition of silane through chemical vapor deposition (CVD). This approach leads to the formation of highly conductive and stable composite anodes. Silicon deposition on the substrate is controlled in terms of the optimal silicon shell thickness, thus enhancing the performance of the cell. These extremely stable, binder-free composite electrodes were characterized as potential anodes in Li-ion batteries, exhibiting long cycle life (>700 cycles), high gravimetric capacity (>4000 mAh/gSi), low irreversible capacity (<10%), and high Coulombic efficiency (>99.5%). These composite anodes meet the requirements of Li-ion batteries for future portable electronics and electric vehicle applications.