The unique physicochemical properties of metallic and magnetic nanowires, whether obtained in well-ordered arrays or as single, isolated, and free-standing structures from patterned templates, have been extensively studied for various technological applications. These applications include magnetic data storage, sensing, biolabeling, barcoding, among many others. Novel template-assisted methods for the synthesis of metallic nanowires offer an enhancement over the control of their shape and morphology, compositional uniformity, and interconnectivity, allowing them for being applied as new metamaterials for novel multifunctional applications. Within this critical review, an extensive overview focused on the synthesis and characterization of the particular properties exhibited by multilayered and multisegmented metallic nanowires having specifically controlled geometries and compositional graded designs through employing electrochemical techniques based on sacrificial nanoporous alumina template-assisted methods, is presented. We review recent advancements in designing synthesis protocols for fabricating new metallic nanowires with multifunctional applications. These protocols offer competitive fabrication costs compared to conventional laboratory procedures, potentially expanding their use in various research areas. In this review, we also establish the new challenges and suggest the future perspectives and expectations that will be covered by these new metamaterial-based nanowires.