The study of iodine in glasses and melts is critical in many areas, from geosciences to materials science to waste management. Glasses in the ternary system Na2O-B2O3-SiO2 were studied with the goal of identifying a glass matrix able to dissolve large quantities of this element, and to identify the main parameters affecting the solubility of iodine. Two sets of experiments were carried out: the first one with the aim of determining the solubility limit of iodine, and the second one to identify the structural variations occurring within the glass network upon iodine incorporation, and to identify the parameters influencing the most both iodine solubility and speciation. We demonstrated that there is a strong dependence of iodine incorporation on bulk chemistry and glass physical properties. A solubility limit of ~5 mol% I has been assessed for B2O3-rich glasses and of ~1 mol% for SiO2-rich ones, and this composition dependence has been explained by considering the fragility parameter of the glass network. Structural variations in the iodine local environment and in the glass network were characterized by Raman, X-ray Absorption Spectroscopy, and 11B NMR. Spectroscopy data point out the coexistence of different I species within the glasses, with iodide being the predominant one, surrounded by Na+ ions.