The spent fuels derived from the nuclear reactor facilities may be finally disposed in a deep underground below 500 m. It majorly has uranium with minor iodine, which is a typical anionic radionuclide. In particular, radioiodine has higher mobility from its spent fuel source. It has been well known that it could freely pass through a compacted bentonite that is one of underground engineering barriers that are used to retard some nuclide’s migration from the spent fuel. We installed a small laboratory apparatus in an anaerobic glove box imitating such an underground repository and evaluated the iodine mobility in compacted bentonites with or without copper. Some copper-bearing bentonites were prepared in two types, a copper ion-exchanged form and a copper nanoparticle-mixed one. In our study, we tried to find an effect of sulfate that has an ability to retard mobile iodine from the compacted bentonite for a long-term period. Conclusively, we found an effective way to limit the iodine release from the compacted bentonite. This condition can be achievable by exchanging the bentonite interlayer cations with copper ions or by simply mixing copper nanoparticles with bentonite powder. In those cases, soluble iodine can be easily immobilized as a solid phase (i.e., marshite (CuI)) by combining with copper via the geochemical role of sulfate and indigenous SRB (sulfate reducing bacteria) of bentonite.