Metal nanowire/polyaniline core-shell nanoparticles have significant potential for the development of materials for electrostatical dissipation, electromagnetic interference shields, chemical and biological sensors, charge and hydrogen storage. In this study, the synthesis of novel core-shell nanostructures of polyaniline-coated copper nanowires (PANI/CuNWs) is presented. CuNWs of 25nm in diameter and several microns in length were synthesised using hard template method and were subsequently coated with doped or undoped polyanilines to obtain high aspect ratio core-shell nanoparticles. SEM, TEM, XPS and electrical conductivity measurements were used to characterise these novel nanomaterials. TEM characterisation showed a smooth polyaniline nanocoating of about 6nm in thickness over the CuNW surface. The thickness of the coating can be controlled by changing PANI concentration in the solution. XPS results indicate that spontaneous adsorption of polyaniline results from the strong surficial interaction between copper atoms at the nanowire surface and imine groups in the polyaniline backbone.