A simple approach for the preparation of core–shell microstructures with an anisotropic shape is proposed in which an Ag nanowire/polyurethane acrylate (AgNW/PUA) composite produced by inverted layer processing is used as a temporary template for the sequential electroless plating of a Cu metal core and Ni shell. Through careful optimization of the metallization conditions, a Cu@Ni core–shell microstructure with an anisotropic shape (i.e., an aspect ratio greater than five) is obtained, which can be easily detached from the template through simple sonication. This technique is therefore considered to be readily applicable to the fabrication of conductive fillers for use in composite structures.