The production of complex structures out of a variety of materials has undergone a revolution due to the rapid development of additive manufacturing (AM) technology. Initially confined to applications such as magnetic actuators and two‐dimensional electric or electronic circuits, the convergence of 3D printing and metallization methods has emerged as a revolutionary approach. This synergy facilitates the creation of functional and customizable metal‐polymer hybrid structures characterized by high strength, lightweight properties, intricate geometric designs, and superior surface finish. These structures also exhibit enhanced electrical and thermal conductivity, as well as optical reflectivity. This paper reviews techniques to improve the effectiveness of 3D‐printed polymer antennas and structures by using various techniques of metallization. The metallization processes are examined, and a classification based on the materials employed is presented to facilitate comparisons that highlight the optimal utilization of materials for the fabrication of 3D‐printed polymer structures. The main emphasis here is on the effectiveness of different processes in terms of deposition, bonding strength, electrical conductivity, and various characteristics of metallic coatings developed on polymers. This review contributes an in‐depth analysis of the latest developments in 3D printing and metallization techniques specifically applied to polymer antennas and structures. The exploration extends to potential applications, challenges encountered, and future prospects within this dynamic field. As AM and metallization continue to evolve, this study aims to provide a comprehensive understanding of the state‐of‐the‐art methodologies and their implications for the future of polymer‐based structures and antennas.