Ion-imprinted polymers (IIPs) are advanced adsorbents featuring selective recognition cavities for targeted metal ion capture, offering a promising route to high-efficiency separation in extractive metallurgy. In the present work, the evolution, design principles, synthesis strategies, separation mechanisms, and practical applicability of IIPs for metal recovery from complex aqueous matrices are overviewed. Key material components, including functional monomers, crosslinkers, template ions, initiators, solvents, and support materials, are discussed in relation to adsorption capacity, selectivity, kinetics, stability, and recyclability. Major preparation routes, such as surface imprinting, bulk polymerization, in situ polymerization, and sol–gel methods, are critically compared to clarify their advantages and limitations. Recent applications for base metals, precious metals, and rare-earth elements demonstrate that IIPs can achieve high specificity and rapid equilibrium under optimized conditions. However, their translation from simulated solutions to real leachates remains constrained by interfering ions, organic contaminants, mass transfer resistance, incomplete template removal, and matrix complexity. Mitigation strategies, including sample pretreatment, improved polymer architecture, and hybrid supports, are therefore emphasized. Additionally, chemometric modelling, machine learning, or artificial intelligence-assisted design may be implemented to advance the prospects of IIPs in industry. Conclusively, IIPs represent a strong separation platform, yet industrial deployment requires robust validation with real feed streams and scalable regeneration protocols during column operation, as well as under chemically aggressive conditions at scale.