As a result of the scarcity of iodine, as well as its threat to the environment if it is present in excess, iodine as a waste needs to be captured. Compared with ion-exchange resins and Ag-containing materials, which are popular iodide adsorbents, Bi-containing compounds show some important advantages, such as high iodide-capture capacity and fast kinetics. In this study, two Bi-containing compounds, BiVO and Bi O , were investigated comprehensively for iodide immobilization. The influence of the pH, iodide/adsorbent ratio, temperature, crystallite size, and competing ions was explored, with a view to optimization of the capture process. Further study of the iodide-adsorbed bismuth compounds confirms that the capture of iodide by BiVO and Bi O is a chemisorption process with the formation of bismuth oxyiodide (Bi O I ). Furthermore, iodide ions are able to penetrate into the bulk of BiVO and Bi O , which is believed to be responsible for their high capture capacity. The application of Bi O I as a photocatalyst has also been examined in Cr reduction. This result makes the capture of iodide by BiVO and Bi O even more environmentally friendly as the photocatalytic application of the iodide-containing adsorbents not only avoids the production of secondary waste but may help to solve other environmental issues.