Methods are provided for fabricating three-dimensional electrically conductive structures. Three-dimensional electrically conductive microstructures are also provided. The method may include providing a mold having at least one microdepression which defines a three-dimensional structure; filling the microdepression of the mold with at least one substrate material; molding the at least one substrate material to form a substrate; and depositing and patterning of at least one electrically conductive layer either during the molding process or subsequent to the molding process to form an electrically conductive structure. In one embodiment, the three-dimensional electrically conductive microstructure comprises an electrically functional microneedle array comprising two or more microneedles, each including a high aspect ratio, polymeric three dimensional substrate structure which is at least substantially coated by an electrically conductive layer.