Arrays of silicon nanowire/multiwalled carbon nanotube nanocomposite have been synthesized by wet etching through electroless metal deposition and chemical vapor deposition. Vertically aligned Si nanowire arrays with controlled diameter and length were fabricated by Ag nanodendrite-assisted wet chemical etching of n-type or p-type silicon wafers using HF/ AgNO3 solution. The composite structure was synthesized by formation of a sheath of carbon multilayers on a Si nanowire template surface through a thermal CVD process under various conditions. The results of Raman spectroscopy, scanning electron microscopy and high resolution transmission electron microcopy reveal that the obtained nanocomposite has a silicon nanowire core/carbon nanotube shell structure. Nanocomposite arrays showed good electrochemical properties.