Electroless copper(Cu) deposition on multi-walled carbon nanotube(MWCNT) activated with silver nitrate was developed and the mechanism was proposed. The Cu/MWCNT hybrid nanowires with MWCNT coated with about 30 nm uniform and continuous crystalline Cu layer which have preferred crystal orientation along the (111) planes were fabricated. Conduction behaviors of the Cu/MWCNT hybrid nanowires demonstrated by electrical measurements and possible reasons were provided. The deposition presents an electroless, simple, and inexpensive process to fabricate Cu/MWCNT hybrid nanowire that may be targeted to connect at specific locations on larger-scale circuits in the near future. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.047202jes] All rights reserved.