<p>Iodine is an essential element widely used in medicine, electronics, and emerging energy technologies, and its efficient separation and speciation are increasingly important for resource recovery and environmental monitoring. In aqueous environments, iodine exists in numerous chemical species, and their interconversion strongly influences its extractability and separation behavior. Among available techniques, solvent extraction is considered one of the most versatile methods for iodine separation due to its operational simplicity, high selectivity, and scalability. This review presents a comprehensive overview of recent advances in the solvent extraction of iodide and related iodine species. First, we briefly outline the speciation of iodine in aqueous systems to clarify how its chemical species controls its extraction behavior. Then, we discuss the principal extraction mechanisms, including the redox-driven extraction of molecular iodine, metal–iodide complex formation, ion-pair extraction with cationic reagents, amine-based extraction, and anion-exchange processes using ionic liquids and related extractants. We also discuss strategies for stripping and recovering iodine species from loaded organic phases. Moreover, recent developments in emerging extraction technologies, such as dispersive liquid–liquid microextraction, liquid membrane systems, and aqueous biphasic systems, are highlighted because they enable enhanced extraction efficiency and analytical sensitivity. Industrial and environmental applications, particularly iodine recovery from natural brines and the separation and analysis of radioiodine, are also discussed. These advances provide a comprehensive framework for understanding and designing selective, efficient, and sustainable iodine separation processes.</p> Graphical abstract <p></p>